JP4821238B2 - Resin composition, polyimide resin composition, polybenzoxazole resin composition, varnish, resin film, and semiconductor device using the same - Google Patents

Description

  The present invention relates to a resin composition, a polyimide resin composition, a polybenzoxazole resin composition, a varnish, a resin film, and a semiconductor device using them.

  Currently, an oxide film (SiOx film) produced by a CVD method (chemical vapor deposition method) or the like is mainly used as an interlayer insulating film for a semiconductor. However, since an inorganic insulating film such as an oxide film has a high dielectric constant, it is difficult to cope with higher speed and higher performance of a semiconductor. Therefore, the application of organic materials has been studied as a low dielectric constant interlayer insulating film. The organic material used for the interlayer insulating film is required to have excellent heat resistance and electrical characteristics and a low dielectric constant.

Conventionally, as an organic material, a polyimide resin, a polyquinoline resin, a polyquinoxaline resin, and the like have been studied (for example, see Patent Document 1).
However, polyimide resins generally have problems such as low heat resistance, high dielectric constant, and high hygroscopicity. Therefore, its application has been limited to some semiconductor elements such as bipolar semiconductor elements in terms of reliability.

  On the other hand, polyquinoline resin and polyquinoxaline resin, which have higher heat resistance, lower dielectric constant, and lower moisture absorption than polyimide resin, are thermoplastic resins, so when exposed to temperatures above the glass transition point of the resin, In some cases, this pattern is deformed and becomes a problem during semiconductor manufacturing.

JP 2000-195853 A

An object of the present invention is to provide a resin composition having high heat resistance and a low dielectric constant, its varnish, a resin film, and a semiconductor device using the same.
Another object of the present invention is to provide a polyimide resin composition, a polybenzoxazole resin composition, their varnishes, a resin film, and a semiconductor device using the same, which have heat resistance and low dielectric constant.

  Such an object is achieved by the present invention described in the following items (1) to (16).

(1) A resin composition comprising a compound having a structure represented by the general formula (1).

［式（１）中、Ａｒは芳香族基を示し、ａは０または１を示す。またＲ₁₁は、水素または炭素数１以上の有機基を示し、ｑが２以上の整数である場合、Ｒ₁₁は互いに同じであっても異なっていても良い。Ｒ₁からＲ₅およびＲ₆からＲ₁₀は、それぞれのベンゼン環において少なくとも１つがＡｒとの結合部位であり、それ以外は、水素、脂環式構造を有する基、該脂環式構造を有する基以外の炭素数１以上１０以下の有機基、ヒドロキシル基およびカルボキシル基のいずれかを示す。また、Ｒ₁₁、Ｒ₁からＲ₅およびＲ₆からＲ₁₀は、少なくとも１つが脂環式構造を有する基を示す。ｑは、１以上の整数である。Ｘは、−Ｏ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＣＯＯ−および−ＯＣＯ−のいずれかを示す。］

[In the formula (1), Ar represents an aromatic group, and a represents 0 or 1. R ₁₁ represents hydrogen or an organic group having 1 or more carbon atoms, and when q is an integer of 2 or more, R ₁₁ may be the same as or different from each other. R ₁ to R ₅ and R ₆ to R ₁₀ each have at least one binding site to Ar in each benzene ring, and other than that, hydrogen, a group having an alicyclic structure, and the alicyclic structure Any one of an organic group having 1 to 10 carbon atoms other than the group, a hydroxyl group and a carboxyl group is shown. R ₁₁ , R ₁ to R ₅ and R ₆ to R ₁₀ each represent a group having an alicyclic structure. q is an integer of 1 or more. X represents any of —O—, —NHCO—, —CONH—, —COO—, and —OCO—. ]

(2) The resin composition according to item (1), wherein a is 1 for the compound having a structure represented by the general formula (1).
(3) The compound having a structure represented by the general formula (1) has an organic group having 1 or more carbon atoms as R ₁₁ , and at least one of the organic groups is a group having an alicyclic structure. The resin composition according to item (1) or item (2).
(4) In the compound having the structure represented by the general formula (1), at least one of each benzene ring is a binding site with Ar as R ₁ to R ₅ and R ₆ to R _{10 in} the formula. In addition, the resin composition according to item (3), which has any one of hydrogen, an organic group having 1 to 10 carbon atoms other than the group having an alicyclic structure, a hydroxyl group, and a carboxyl group. object.
(5) In the compound having the structure represented by the general formula (1), a is 0, and at least one of each of the benzene rings is Ar as R ₁ to R ₅ and R ₆ to R ₁₀ Other than that, hydrogen, a group having an alicyclic structure, an organic group having 1 to 10 carbon atoms other than the group having the alicyclic structure, a hydroxyl group and a carboxyl group The resin composition according to item (1), wherein at least one has a group having the alicyclic structure.
(6) The compound having the structure represented by the general formula (1) has a group selected from the structure represented by the general formula (2) as Ar in the general formula (1). Item 5. The resin composition according to any one of Items (5).

［式中、Ｙは、−Ｏ−、−Ｓ−、−ＯＣＯ−および−ＣＯＯ−のいずれかを示す。］

[Wherein Y represents any of —O—, —S—, —OCO— and —COO—. ]

(7) The resin composition according to any one of (1) to (6), wherein the group having an alicyclic structure is a group having an adamantane structure.
(8) The resin composition according to item (7), wherein the group having an adamantane structure has an alkyl group having 1 to 20 carbon atoms.
(9) The compound having the structure represented by the general formula (1) has —NHCO— as X in the general formula (1), and has a carboxyl group as R ₂ or R ₃ , and R ₇ or R _8. The resin composition according to any one of Items (1) to (8).
(10) The compound having the structure represented by the general formula (1) has —NHCO— as X in the general formula (1), and a hydroxyl group as R ₂ or R ₃ , and R ₇ or R _8. The resin composition according to any one of Items (1) to (8).
(11) The resin according to any one of items (1) to (10) obtained by dehydrating and ring-closing the compound having the structure represented by the general formula (1) in the resin composition Composition.
(12) A polyimide resin composition obtained by dehydrating and cyclizing a compound having a structure represented by the general formula (1) in the resin composition according to item (9).
(13) A polybenzoxazole resin composition obtained by dehydrating and cyclizing a compound having the structure represented by the general formula (1) in the resin composition according to item (10).
(14) The resin composition according to any one of items (1) to (11), the polyimide resin composition according to item (12), or the polybenzoxazole resin composition according to item (13) Varnish obtained from things.
(15) The resin composition according to any one of items (1) to (11), the polyimide resin composition according to item (12), and the polybenzoxazole resin composition according to item (13) A resin film obtained by heat-treating a product or a varnish according to item (14).
(16) A semiconductor device comprising the resin film according to item (15).

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which comprises the resin film which becomes high heat resistance and low dielectric constant after heat processing, its varnish, a resin film, and a semiconductor device using the same can be obtained.
According to the invention, a polyimide resin precursor composition excellent in heat resistance can be obtained when a polyimide resin is used, and a benzoxazole resin precursor composition excellent in heat resistance can be obtained when a polybenzoxazole resin is used. be able to.
In addition, according to the present invention, it is possible to obtain a polyimide resin composition, a polybenzoxazole resin composition, a varnish thereof, a resin film, and a semiconductor device using the same, which have heat resistance and low dielectric constant.

Hereinafter, the best mode for carrying out the resin composition, polyimide resin composition, polybenzoxazole resin composition, resin film and semiconductor device of the present invention will be described.
The resin composition of this invention contains the compound which has a structure represented by General formula (1). Thereby, the resin film which is excellent in heat resistance and has a low dielectric constant can be obtained. The compound having the structure represented by the general formula (1) includes a polyimide resin precursor, a polybenzoxazole resin precursor, and the like.

  The compound having a structure represented by the general formula (1) used in the present invention has an aromatic group as Ar in the general formula (1). Examples of the aromatic group include a phenyl group, Naphthyl group, anthracenyl group, phenanthrenyl group, polycyclic aromatic group having 4 or more aromatic rings, fluorenyl group, diphenylfluorenyl group, biphenyl group, pyridyl group, dipyridyl group, polycyclic aromatic group containing nitrogen Group etc. are mentioned, Especially the group which has a structure represented by General formula (2) is preferable. Thereby, good solubility in a solvent used when a resin film and a semiconductor device including the resin film can be provided.

  Examples of Y in the general formula (2) include —O—, —S—, —OCO—, and —COO—, and —O— is particularly preferable in terms of solubility in a solvent and heat resistance.

Further, the compound having the structure represented by the general formula (1) is one in which at least one of R ₁ to R ₅ and R ₆ to R ₁₀ is a binding site with Ar in each benzene ring, Other than that, it has any one of hydrogen, a group having an alicyclic structure, an organic group having 1 to 10 carbon atoms other than the group having the alicyclic structure, a hydroxyl group, and a carboxyl group. Examples of the group having an alicyclic structure include the same groups as R ₁₁ described later. Examples of the organic group having 1 to 10 carbon atoms other than the group having an alicyclic structure include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a heptyl group, A hexyl group, a pentyl group, an octyl group, a nonyl group, a decyl group, etc., and those obtained by substituting these organic groups with fluorine, such as a fluoromethyl group, can be mentioned.

In addition, the compound having the structure represented by the general formula (1) can have an organic group having 1 or more carbon atoms as R ₁₁ , other than hydrogen. Examples thereof include a group having an alicyclic structure and an organic group having 1 to 10 carbon atoms other than the group having the alicyclic structure. When these organic groups are included, at least one group having an alicyclic structure It is preferable to have. Examples of the group having an alicyclic structure include a group having a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, a norbornene structure, an adamantane structure, and the like, and particularly, an adamantane structure. It is preferably a group. The group having an adamantane structure has a structure having an adamantane structure as a minimum unit, for example, an adamantyl group, a diamantyl group, a triamantyl group, a tetramantyl group, a pentamantyl group, a hexamantyl group, a heptamantyl group, an octamantyl group, a nonamantyl group A group having an (aliphatic) polycyclic skeleton structure such as a group, a decamantyl group and an undecamantyl group, and further a group having a plurality of groups having the polycyclic skeleton structure. Examples of the group having a plurality of groups having a polycyclic skeleton structure include groups having an oligo structure or a poly structure. In the case of an adamantyl group as the group having the polycyclic skeleton structure, for example, di ( 1,3-adamantane) group and di (2,2-adamantane) group such as biadamantyl group, tri (1,3-adamantane) group and tri (2,2-adamantane) group such as triadamantyl group, tetra ( Tetraadamantyl groups such as 1,3-adamantane) group and tetra (2,2-adamantane) group, pentaadamantyl groups such as penta (1,3-adamantane) group and penta (2,2-adamantane) group, hepta ( 1,3-adamantane) group and heptaadamantyl group such as hepta (2,2-adamantane) group, hexaadamantyl group, octaa Examples include a group having an oligoadamantane structure such as a mantyl group, nonaadamantyl group, decaadamantyl group, and undecaadamantyl group, and a group having a polyadamantane structure having a large number of adamantyl groups, and the polycyclic skeleton. In the case of a group other than an adamantyl group as the group having a structure, a group in which the adamantyl group is substituted in the group having the oligoadamantane structure or the group having a polyadamantane structure, for example, a di- (diamantane) group, a tri- (Diamantane) group, tetra- (diamantane) group, penta- (diamantane) group, hexa- (diamantane) group, hepta- (diamantane) group, octa- (diamantane) group, nona- (diamantane) group, deca- ( Diamantane) and undeca (diamantane) groups, A group having a plurality of diamantane groups, di- (triamantane) group, tri- (triamantane) group, tetra- (triamantane) group, penta- (triamantane) group, hexa- (triamantane) group, hepta A group having a plurality of triamantane groups such as-(triamantane) group, octa- (triamantane) group, nona- (triamantane) group, deca- (triamantane) group and undeca- (triamantane) group, Di- (tetraamantane) group, tri- (tetraamantane) group, tetra- (tetraamantane) group, penta- (tetraamantane) group, hexa- (tetraamantane) group, hepta- (tetraamant) Tan) group, octa- (tetraamantane) group, nona- (tetraamantane) group, deca (tetraamantane) group and undeca (te And a group having a plurality of tetraamantane groups such as a (traamantane) group. Among these, an adamantyl group, a diamantyl group, a triamantyl group, a tetramantyl group, a pentamantyl group, a hexamantyl group, a heptamantyl group, an octamantyl group, a nonamantyl group, a decamantyl group, an undecamantyl group, a biadamantyl group, a triadamantyl group, a tetraadamantyl group , Pentaadamantyl group, hexaadamantyl group, heptaadamantyl group, octaadamantyl group, nonaadamantyl group, decaadamantyl group and undecaadamantyl group are preferable, adamantyl group, diamantyl group, triamantyl group, tetramantyl group, pentamantyl group, di (1 , 3-adamantane) group, tri (1,3-adamantane group), tetra (1,3-adamantane) group, penta (1,3-adamantane) group, di (2,2-adame) Pentane) group, tri (2,2-adamantane) group, tetra (2,2-adamantane) group and penta (2,2-adamantane) group are more preferable. By introducing an adamantane structure as R ₁₁ , the low dielectric constant and moisture resistance can be improved without lowering the heat resistance and the solubility in a solvent. The group having an adamantane structure is bonded to an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a fluoroalkyl group such as a fluoromethyl group, a fluoroethyl group, a fluoropropyl group and a fluorobutyl group. Also good. By introducing an alkyl group into the adamantane structure, solubility in a solvent and heat resistance can be improved.
As for R ₁₁ , the organic group having 1 or more carbon atoms other than the group having an alicyclic structure is the same as the organic group having 1 to 10 carbon atoms as R ₁ to R ₅ and R ₆ to R ₁₀ . Those are preferred.

The compound having the structure represented by the general formula (1) has at least one group having an alicyclic structure as R ₁₁ , R ₁ to R ₅ and R ₆ to R ₁₀ , and Ar is aromatic. When no group is present, at least one of R ₁ to R ₅ and R ₆ to R ₁₀ has a group having the alicyclic structure. In this case, the dielectric constant can be further reduced, and the heat resistance, particularly the glass transition temperature, becomes more excellent.

  Moreover, the compound which has a structure represented by General formula (1) has either -O-, -NHCO-, -CONH-, -COO-, and -OCO- as X.

In the compound having the structure represented by the general formula (1) used in the present invention, in the formula, when -O- is present as X, when polyphenylene ether has -NHCO- or -CONH- as X, When the polyamide has —COO— or —OCO— as X, it can be used as a polyester.
In the above structure, particularly in the case of polyamide, when R ₂ or R ₃ and R ₇ or R _{8 have} a carboxyl group, the compound having the structure represented by the general formula (1) is a polyimide resin precursor. It becomes a structure. When R ₂ or R ₃ and R ₇ or R ₈ are hydroxyl groups, the compound having the structure represented by the general formula (1) has a polybenzoxazole resin precursor structure. When these structures are selected, the heat resistance can be further improved. For example, when X is —NHCO—, R ₇ or R ₈ has a hydroxyl group, R ₂ or R ₃ has an amino group, R ₆ or R ₉ , and R ₅ are alicyclic. Examples thereof include a structure in which Ar is bonded to R ₁ or R ₄ and R ₁₀ .

When the compound having the structure represented by the general formula (1) has a structure of a polyimide resin precursor, it can be made into a polyimide resin by dehydrating and ring-closing the compound.
Moreover, when it becomes a polybenzoxazole resin precursor structure, it can be set as polybenzoxazole resin by dehydrating and ring-closing this.

  As a method for producing the polyimide resin precursor, for example, it can be obtained by reacting a tetracarboxylic dianhydride and a diamine compound. As the reaction method, after acid dianhydride is half-esterified with alcohols, it may be reacted with a diamine compound.

  Examples of the tetracarboxylic dianhydride include those having a structure represented by the following general formula (3) as those having an alicyclic structure.

式（３）中、Ａｒは芳香族基を示し、aは０または１を示す。またＲ₂₀は、水素または炭素数１以上の有機基を示し、ｑが２以上の整数である場合、Ｒ₂₀は互いに同じであっても異なっていても良い。Ｒ₁₂からＲ₁₅およびＲ₁₆からＲ₁₉は、それぞれのベンゼン環において少なくとも１つがＡｒとの結合部位であり、それ以外は、水素、脂環式構造を有する基、該脂環式構造を有する基以外の炭素数１以上１０以下の有機基のいずれかを示す。また、Ｒ₂₀、Ｒ₁₂からＲ₁₅およびＲ₁₆からＲ₁₉は、少なくとも１つが脂環式構造を有する基を示す。ｑは、１以上の整数である。上記芳香族基、炭素数１以上の有機基、脂環式構造を有する基、該脂環式構造を有する基以外の炭素数１以上１０以下の有機基は、一般式（１）におけるものと同様の基を示す。

In formula (3), Ar represents an aromatic group, and a represents 0 or 1. R ₂₀ represents hydrogen or an organic group having 1 or more carbon atoms, and when q is an integer of 2 or more, R ₂₀ may be the same as or different from each other. R ₁₂ to R ₁₅ and R ₁₆ to R ₁₉ each have at least one binding site to Ar in each benzene ring, and the others have hydrogen, a group having an alicyclic structure, and the alicyclic structure. Any of organic groups having 1 to 10 carbon atoms other than the group is shown. R ₂₀ , R ₁₂ to R ₁₅ and R ₁₆ to R ₁₉ each represent a group having an alicyclic structure. q is an integer of 1 or more. The aromatic group, the organic group having 1 or more carbon atoms, the group having an alicyclic structure, and the organic group having 1 to 10 carbon atoms other than the group having the alicyclic structure are the same as those in the general formula (1). Similar groups are shown.

Specific examples of the tetracarboxylic dianhydride having the alicyclic structure include 9,9-bis (3,4-dicarboxyphenyl) -2,7-diadamantyl-fluorene-dianhydride, 9,9. -Bis [4- (3,4-dicarboxyphenoxy) -phenyl] -2,7-diadamantyl-fluorene-dianhydride and 9,9-bis [4- (3,4-dicarboxy-5-adamantyl) Tetracarboxylic dianhydrides having an adamantane structure and a fluorene structure, such as phenoxy) -phenyl] -fluorene-dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) -4,6-diadamantyl-benzene Adamantane and benzene structures such as dianhydrides and 1,3-bis (3,4-dicarboxy-5-adamantylphenoxy) -benzene-dianhydrides Tetracarboxylic dianhydride, a tetracarboxylic dianhydride having an adamantane structure and a naphthalene structure, a tetracarboxylic dianhydride having an adamantane structure and an anthracene structure, 2,2′-bis ((3,4-dicarboxyl Adamantane and biphenyl structures such as phenoxy) -5,5′-diadamantyl-biphenyl-dianhydride and 2,2′-bis ((3,4-dicarboxy-5-adamantylphenoxy) -biphenyl-dianhydride) In the group having an alicyclic structure, a structure having the adamantane structure described above as a minimum unit can be selected as the adamantane structure. May be arbitrarily selected within the range included in the general formula (1).
Moreover, when using the diamine compound which has group which has alicyclic structure, what does not have group which has alicyclic structure in these tetracarboxylic dianhydrides can be used. Examples of the tetracarboxylic dianhydride having no alicyclic structure include 9,9-bis (3,4-dicarboxyphenyl) fluorene-dianhydride, 9,9-bis [4- (3 , 4-Dicarboxyphenoxy) -phenyl] fluorene-dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene-dianhydride, 2,2′-bis ((3,4-dicarboxy) And phenoxy) biphenyl dianhydride.

  The tetracarboxylic dianhydride having the adamantane structure and fluorene structure can be synthesized, for example, by the following method. First, Suzuki coupling reaction between 2-bromo-5- (1-adamantyl) -toluene and 4- (1-adamantyl) -benzeneboronic acid, followed by fluorenation reaction, fluorenonation reaction, the corresponding 2,7 -Diadamantylfluorenone was synthesized and subjected to dehydration reaction with o-xylene. Further, a phthalic acid structure was formed by oxidation reaction of methyl group, and then 9,9-bis (3 , 4-Dicarboxy-phenyl) -2,7-diadamantyl-fluorene dianhydride can be synthesized. Further, fluorene bisphenol having an adamantyl group is obtained by dehydration reaction of 2,7-diadamantylfluorenone and phenol, and this is reacted with dimethyl 4-fluoro-phthalate to be etherified. Further, a phthalic acid structure is obtained by alkali hydrolysis and acid treatment, and 9,9-bis [(3,4-dicarboxy-phenoxy) -phenyl] -2,7-diadamantyl-fluorene is obtained by a dehydration reaction with acetic anhydride or the like. A dianhydride can be synthesized.

  The tetracarboxylic dianhydride having an adamantane structure and a benzene structure can be synthesized, for example, by the following method. First, dihydroxybenzene having an adamantane structure is synthesized from the reaction of resorcinol and 1-bromoadamantane. This is etherified with 4-fluoro-dimethyl phthalate. Further, a phthalic acid structure is obtained by alkaline hydrolysis and acid treatment, and then 1,3-bis (3,4-dicarboxy-phenoxy) -4,6-diadamantyl-benzene dianhydride by a dehydration reaction with acetic anhydride or the like. You can synthesize things.

  The tetracarboxylic dianhydride having the adamantane structure and the biphenyl structure can be synthesized, for example, by the following method. First, dihydroxy-biphenyl having an adamantyl group is synthesized from the reaction of 2,2'-dihydroxy-biphenyl and 1-bromo-adamantane. This is etherified with 4-fluoro-dimethyl phthalate. Further, phthalic acid structure is obtained by alkaline hydrolysis and acid treatment, and then 2,2′-bis (3,4-dicarboxy-phenoxy) -5,5′-diadamantyl-biphenyl by dehydration reaction with acetic anhydride or the like. Diacid anhydride can be synthesized.

  Examples of the diamine compound include those having a structure represented by the following general formula (4) as those having an alicyclic structure.

式（４）中、Ａｒは芳香族基を示し、aは０または１を示す。またＲ₃₁は、水素または炭素数１以上の有機基を示し、ｑが２以上の整数である場合、Ｒ₃₁は互いに同じであっても異なっていても良い。Ｒ₂₁からＲ₂₅およびＲ₂₆からＲ₃₀は、それぞれのベンゼン環において少なくとも１つがＡｒとの結合部位であり、それ以外は、水素、脂環式構造を有する基、該脂環式構造を有する基以外の炭素数１以上１０以下の有機基のいずれかを示す。また、Ｒ₃₁、Ｒ₂₁からＲ₂₅およびＲ₂₆からＲ₃₀は、少なくとも１つが脂環式構造を有する基を示す。ｑは、１以上の整数である。上記芳香族基、炭素数１以上の有機基、脂環式構造を有する基、該脂環式構造を有する基以外の炭素数１以上１０以下の有機基は、一般式（１）におけるものと同様の基を示す。

In formula (4), Ar represents an aromatic group, and a represents 0 or 1. R ₃₁ represents hydrogen or an organic group having 1 or more carbon atoms. When q is an integer of 2 or more, R ₃₁ may be the same as or different from each other. R ₂₁ to R ₂₅ and R ₂₆ to R ₃₀ each have at least one binding site to Ar in each benzene ring, and the others have hydrogen, a group having an alicyclic structure, and the alicyclic structure. Any of organic groups having 1 to 10 carbon atoms other than the group is shown. R ₃₁ , R ₂₁ to R ₂₅ and R ₂₆ to R ₃₀ each represent a group having an alicyclic structure. q is an integer of 1 or more. The aromatic group, the organic group having 1 or more carbon atoms, the group having an alicyclic structure, and the organic group having 1 to 10 carbon atoms other than the group having the alicyclic structure are the same as those in the general formula (1). Similar groups are shown.

Specific examples of the diamine compound having an alicyclic structure include 2,7-di (1-adamantyl) -fluorene-9,9-bis (4-aniline), 9,9-bis (4-amino-5). Diamine compounds having an adamantane structure and a fluorene structure such as -adamantylphenyl) -fluorene and 9,9-bis [(4-aminophenoxy) -phenyl] -2,7-diadamantyl-fluorene, 4,6-di (1 Adamantane structure such as adamantyl) -1,3-bis (4-aminophenoxy) -benzene, 1,3-bis (4-amino-5-adamantylphenoxy) -benzene, a diamine compound having a benzene structure, an adamantane structure, Diamine compound having naphthalene structure, diamine compound having adamantane structure and anthracene structure, 2 Adamantane and biphenyl structures such as 2'-bis (4-aminophenoxy) -5,5'-di (1-adamantyl) -biphenyl, 2,2'-bis (4-amino-5-adamantylphenoxy) -biphenyl In the group having an alicyclic structure, a structure having the above-mentioned adamantane structure as the minimum unit can be selected. The bonding position of the adamantane structure may be arbitrarily selected within the range included in the general formula (1).
Moreover, when using tetracarboxylic dianhydride which has group which has alicyclic structure, what does not have group which has alicyclic structure in these diamine compounds can be used. Examples of the diamine compound having no alicyclic structure include 9,9-bis (4-aniline) fluorene, 9,9-bis [(4-aminophenoxy) -phenyl] fluorene, and 1,3-bis. (4-aminophenoxy) -benzene, 2,2′-bis (4-aminophenoxy) biphenyl and the like.
In the combination of the tetracarboxylic dianhydride and the diamine compound, it is preferable that both have a group having an alicyclic structure in order to further reduce the dielectric constant and obtain a polyimide resin excellent in heat resistance.

  The diamine compound having an adamantane structure and a fluorene structure can be synthesized, for example, by the following method. First, Suzuki coupling reaction between 2-bromo-5- (1-adamantyl) -toluene and 4- (1-adamantyl) -benzeneboronic acid, followed by fluorenation reaction, fluorenonation reaction, the corresponding 2,7 -Diadamantylfluorenone is synthesized, and 9,9-bis (4-amino-phenyl) -2,7-di (1-adamantyl) -fluorene can be synthesized by dehydration reaction with aniline. Further, fluorene bisphenol having an adamantyl group is obtained by dehydration reaction of 2,7-diadamantylfluorenone and phenol, and etherified with 4-fluoro-nitrobenzene, and further subjected to a reduction reaction, thereby obtaining 9 , 9-bis [(4-aminophenoxy) -phenyl] -2,7-di (1-adamantyl) -fluorene can be synthesized.

  The diamine compound having an adamantane structure and a benzene structure can be synthesized, for example, by the following method. First, dihydroxybenzene having an adamantane structure is synthesized by a reaction between resorcinol and 1-bromoadamantane. 4,6-Di (1-adamantyl) -1,3-bis (4-aminophenoxy) -benzene can be synthesized by etherification with 4-fluoro-nitrobenzene and further reduction reaction.

The diamine compound having an adamantane structure and a biphenyl structure can be synthesized, for example, by the following method. First, dihydroxy-biphenyl having an adamantyl group is synthesized from the reaction of 2,2′-dihydroxy-biphenyl and 1-bromo-adamantane. This was etherified with 4-fluoro-nitrobenzene and further subjected to a reduction reaction to synthesize 2,2′-bis (4-aminophenoxy) -5,5′-di (1-adamantyl) -biphenyl. it can.
Moreover, in these synthesis | combination, it can also copolymerize or blend using tetracarboxylic dianhydride and diamine compounds other than said tetracarboxylic dianhydride and diamine compound.

  As a method for producing the polybenzoxazole resin precursor, for example, it can be obtained by reacting a bis o-aminophenol compound and a dicarboxylic acid compound by a method such as an acid chloride method or an active ester method.

As said bis-o-aminophenol compound, what has a structure represented by the said General formula (3) is mentioned as what has an alicyclic structure.
Specific examples of the bis o-aminophenol compound having the alicyclic structure include 9,9-bis (3-amino-4-hydroxy-phenyl) -2,7-di (1-adamantyl) -fluorene, 9 , 9-bis (3-amino-4-hydroxy-5-adamantylphenyl) -fluorene, 9,9-bis (3-amino-4-hydroxy-phenyl) -2,7-di (3,5-dimethyl- 1-adamantyl) -fluorene, 9,9-bis [(3-hydroxy-4-aminophenoxy) -phenyl] -2,7-di (1-adamantyl) -fluorene, 9,9-bis [(3-hydroxy -4-amino-5-adamantylphenoxy) -phenyl] -fluorene, 9,9-bis [(3-hydroxy-4-aminophenoxy) -phenyl] -2,7-di (3,5-di Adamantane and fluorene structures such as til-1-adamantyl) adamantyl-fluorene and 9,9-bis [4- (4-amino-3-hydroxy-6-adamantyl-phenoxy) -phenyl] -2,7-fluorene; Bisaminophenol compound having 1,3-bis (3-hydroxy-4-aminophenoxy) -4,6-diadamantyl-benzene, 1,3-bis (3-hydroxy-4-amino-5-adamantylphenoxy) ) -Benzene, 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene, 4,6-di (3,5-dimethyl-1-adamantyl) -1 , 3-bis (4-amino-3-hydroxyphenoxy) benzene, 4,6-di (3- (3,5-dimethyl-1-adaman) )-(3,5-dimethyl-1-adamantyl))-1,3-bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxy-6-adamantyl) Bisaminophenol having an adamantane structure and a benzene structure, such as -phenoxy) benzene and 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxy-6-adamantyl-phenoxy) benzene Compound, bisaminophenol compound having adamantane structure and naphthalene structure, bisaminophenol compound having adamantane structure and anthracene structure, 2,2′-dihydroxy-3,3′-diamino-5,5′-diadamantyl- Biphenyl, 2,2′-dihydroxy-3,3′-diamino-5,5′-bis (3,5- Dimethyl-1-adamantyl) -biphenyl, 2,2′-dihydroxy-3,3′-diamino-5,5′-bis (3- (5,7-dimethyl-1-adamantyl)-(3,5-dimethyl -1-adamantyl)) biphenyl, 2,2′-bis (3-hydroxy-4-aminophenoxy) -5,5′-diadamantyl-biphenyl, 2,2′-bis (3-hydroxy-4-amino-) 5-adamantylphenoxy) -biphenyl, 2,2′-bis [4- (3-hydroxy-4-amino) phenoxy] -5,5′-bis (3- (3,5-dimethyl-1-adamantyl) biphenyl ), 2,2′-bis [4- (3-hydroxy-4-amino) phenoxy-phenyl] -5,5′-bis (3- (3,5-dimethyl-1-adamantyl) biphenyl, 2,2 '-Bis [4- ( -Amino-3-hydroxy-6-adamantyl) phenoxy] -biphenyl and 2,2′-bis [4- (4-amino-3-hydroxy-6-adamantyl) phenoxy] -5,5′-bis (1- Bisaminophenol compounds having an adamantane structure and a biphenyl structure such as adamantyl) biphenyl, and the like. In the group having an alicyclic structure, the structure having the adamantane structure described above as the minimum unit is selected. Can do. The bonding position of the adamantane structure may be arbitrarily selected within the range included in the general formula (1).
Moreover, when using the dicarboxylic acid compound which has group which has alicyclic structure, what does not have group which has alicyclic structure in these bis o-aminophenol compounds can be used. Examples of the bis o-aminophenol compound having no group having an alicyclic structure include 9,9-bis (3-amino-4-hydroxy-phenyl) fluorene and 9,9-bis (3-amino-4-). Hydroxy-phenyl) fluorene, 1,3-bis (3-hydroxy-4-aminophenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, 2,2'-dihydroxy-3,3 Examples include '-diaminobiphenyl and 2,2'-bis [4- (3-hydroxy-4-amino) phenoxy] biphenyl.

  The bisaminophenol compound having an adamantane structure and a fluorene structure can be synthesized, for example, by the following method. First, Suzuki coupling reaction between 2-bromo-5- (1-adamantyl) -toluene and 4- (1-adamantyl) -benzeneboronic acid, followed by fluorenation reaction, fluorenonation reaction, the corresponding 2,7 -Diadamantyl fluorenone is synthesized, and fluorene bisphenol having an adamantyl group is obtained by dehydration reaction with phenol. 9,9-bis (3-amino-4-hydroxy-phenyl) -2,7-diadamantyl-fluorene is synthesized by nitration of the ortho position of the hydroxyl group and further reduction to the amino group. it can. The fluorene bisphenol having an adamantyl group obtained above is etherified with 2-benzyloxy-4-fluoro-nitrobenzene, and further subjected to deprotection and reduction reaction, whereby 9,9-bis [(3-hydroxy -4-aminophenoxy) -phenyl] -2,7-diadamantyl-fluorene can be synthesized.

  The bisaminophenol compound having an adamantane structure and a benzene structure can be synthesized, for example, by the following method. First, dihydroxybenzene having an adamantane structure is synthesized by a reaction between resorcinol and 1-bromoadamantane or 1-bromo-3,5-dimethyladamantane. This was etherified with 2-benzyloxy-4-fluoro-nitrobenzene and further deprotected and reduced to give 1,3-bis (3-hydroxy-4-aminophenoxy) -4,6-di Adamantyl-benzene or 4,6-di (3,5-dimethyl-1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene can be synthesized.

The bisaminophenol compound having an adamantane structure and a biphenyl structure can be synthesized, for example, by the following method. First, dihydroxy-biphenyl having an adamantyl group is synthesized from the reaction of 2,2′-dihydroxy-biphenyl and 1-bromoadamantane or 1-bromo-3,5-dimethyladamantane. By performing nitration at the ortho position of the hydroxyl group and further reduction to the amino group, 2,2′-dihydroxy-3,3′-diamino-5,5′-diadamantyl-biphenyl or 2,2 '-Dihydroxy-3,3'-diamino-5,5'-di (3,5-dimethyl-1-adamantyl) -biphenyl can be synthesized.
Further, the dihydroxy-biphenyl having an adamantyl group obtained above is etherified with 2-benzyloxy-4-fluoro-nitrobenzene, and further subjected to deprotection and reduction reaction, whereby 2,2′-bis (3 -Hydroxy-4-aminophenoxy) -5,5'-diadamantyl-biphenyl or 4,6-di (3,5-dimethyl-1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) ) Can synthesize benzene.

As said dicarboxylic acid compound, what has a structure represented by the said General formula (4) is mentioned as what has an alicyclic structure.
Specific examples of the dicarboxylic acid compound having an alicyclic structure include 2,7-diadamantylfluorene-9,9-bisbenzoic acid, 9,9-bis (4-carboxy-3-adamantylphenyl) fluorene, 2 , 7-di (3,5-dimethyl-1-adamantyl) fluorene-9,9-bisbenzoic acid, 9,9-bis (4-carboxy-phenyl) -2,7-diadamantyl-fluorene, 9,9 -Bis (4-carboxy-phenyl) -2,7-di (3,5-dimethyl-1-adamantyl) -fluorene, 9,9-bis [(4-carboxy-phenoxy) -phenyl] -2,7- Diadamantyl-fluorene, 9,9-bis [(4-carboxy-3-adamantylphenoxy) -phenyl] -fluorene and 9,9-bis [(4-carboxy-phen A dicarboxylic acid having an adamantane structure and a fluorene structure, such as xyl) -phenyl] -2,7-di (3,5-dimethyl-1-adamantyl) -fluorene, 4,6-di [(3- (5,7 -Dimethyl-1-adamantyl)-(3,5-dimethyl-1-adamantyl))-1,3-bis (4-carboxy-phenoxy) benzene, 1,3-bis (4-carboxy-3-adamantylphenoxy) Benzene, 1,3-bis (4-carboxyl-phenoxy) -4,6-diadamantyl-benzene and 1,3-bis (4-carboxyl-phenoxy) -4,6-di (3,5-dimethyl-1 -Adamantyl) -dicarboxylic acid having adamantane structure and benzene structure, such as benzene, dicarboxylic acid having adamantane structure and naphthalene structure Dicarboxylic acid having an adamantane structure and an anthracene structure, 2,2′-bis [(4-carboxy-phenoxy) -phenyl] -5,5′-bis [3- (1-adamantyl)-(1-adamantyl)] -Biphenyl, 2,2'-bis [(4-carboxy-3-adamantylphenoxy) -phenyl] -biphenyl, 2,2'-bis (4-carboxy-phenoxy) -5,5'-diadamantyl-biphenyl and Dicarboxylic acids having an adamantane structure such as 2,2′-bis (4-carboxy-phenoxy) -5,5′-di (3,5-dimethyl-1-adamantyl) -biphenyl and a biphenyl structure, 3- (2 -(1-adamantyl) ethynyl) phthalic acid, 3- (2- (2-adamantyl) ethynyl) phthalic acid, 4- (2- (1-adamantyl) e Nyl) phthalic acid, 4- (2- (2-adamantyl) ethynyl) phthalic acid, 3- (2- (1- (3,5-dimethyladamantyl)) ethynyl) phthalic acid, 3- (2- (2- (1,3-dimethyladamantyl)) ethynyl) phthalic acid, 4- (2- (1- (3,5-dimethyladamantyl)) ethynyl) phthalic acid, 4- (2- (2- (1,3-dimethyl) Phthalic acid having an adamantane structure and an ethynyl structure such as adamantyl)) ethynyl) phthalic acid, 4- (2- (1-adamantyl) ethynyl) isophthalic acid, 4- (2- (2-adamantyl) ethynyl) isophthalic acid, 5- (2- (1-adamantyl) ethynyl) isophthalic acid, 5- (2- (2-adamantyl) ethynyl) isophthalic acid, 4- (2- (1- (3,5-dimethyladamantyl)) Ethynyl) isophthalic acid, 4- (2- (2- (1,3-dimethyladamantyl)) ethynyl) isophthalic acid, 5- (2- (1- (3,5-dimethyladamantyl)) ethynyl) isophthalic acid, 5 -(2- (2- (1,3-dimethyladamantyl)) ethynyl) isophthalic acid such as isophthalic acid having an adamantane structure and ethynyl structure, 5- (2- (1-adamantyl) ethynyl) terephthalic acid, 5- (2- (2-adamantyl) ethynyl) terephthalic acid, 5- (2- (1- (3,5-dimethyladamantyl)) ethynyl) terephthalic acid, 5- (2- (2- (1,3-dimethyladamantyl) )) Ethynyl) terephthalic acid having an adamantane structure and ethynyl structure such as terephthalic acid, 3- (2- (1-diamantyl) ethynyl) phthalic acid Diamantyl structures such as 3- (2- (2-diamantyl) ethynyl) phthalic acid, 4- (2- (1-diamantyl) ethynyl) phthalic acid, 4- (2- (2-diamantyl) ethynyl) phthalic acid, and ethynyl 4- (2- (1-diamantyl) ethynyl) isophthalic acid, 4- (2- (2-diamantyl) ethynyl) isophthalic acid, 5- (2- (1-diamantyl) ethynyl) isophthalic acid having the structure Acid, isophthalic acid having a diamantyl structure and an ethynyl structure such as 5- (2- (2-diamantyl) ethynyl) isophthalic acid, 5- (2- (1-diamantyl) ethynyl) terephthalic acid, 5- (2- ( Terephthalic acid having a diamantyl structure such as 2-diamantyl) ethynyl) terephthalic acid and an ethynyl structure, 3- (2- (1-teto) Mantyl) ethynyl) phthalic acid, 3- (2- (2-tetramantyl) ethynyl) phthalic acid, 4- (2- (1-tetramantyl) ethynyl) phthalic acid, 4- (2- (2-tetraamantyl) ethynyl ) Phthalic acid having a tetramantyl structure such as phthalic acid and an ethynyl structure, 4- (2- (1-tetramantyl) ethynyl) isophthalic acid, 4- (2- (2-tetramantyl) ethynyl) isophthalic acid, 5- (2 -(1-tetramantyl) ethynyl) isophthalic acid, 5- (2- (2-tetramantyl) ethynyl) isophthalic acid and other isophthalic acid having a tetramantyl structure and an ethynyl structure, 5- (2- (1-tetramantyl) ethynyl) Tetramantyl structures such as terephthalic acid and 5- (2- (2-tetramantyl) ethynyl) terephthalic acid Terephthalic acid having a tinyl structure, 3- (2- (3- (1,1′-biadamantyl)) ethynyl) phthalic acid, 3- (2- (2- (1,1′-biadamantyl)) ethynyl ) Phthalic acid, 4- (2- (3- (1,1′-biadamantyl)) ethynyl) phthalic acid, 4- (2- (2- (1,1′-biadamantyl)) ethynyl) phthalic acid, 3- (2- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) ethynyl) phthalic acid, 3- (2- (2- (1,1 ′ -(3,5,3 ', 5'-tetramethylbiadamantyl))) ethynyl) phthalic acid, 4- (2- (7- (1,1'-(3,5,3 ', 5'-tetra) Methylbiadamantyl))) ethynyl) phthalic acid, 4- (2- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl)))) Isophthalic acid having a biadamantyl structure and an ethynyl structure such as (thinyl) phthalic acid, 4- (2- (3- (1,1′-biadamantyl)) ethynyl) isophthalic acid, 4- (2- (2- (2- ( 1,1′-biadamantyl)) ethynyl) isophthalic acid, 5- (2- (3- (1,1′-biadamantyl)) ethynyl) isophthalic acid, 5- (2- (2- (1,1 ′) -Viadamantyl)) ethynyl) isophthalic acid, 4- (2- (7- (1,1 '-(3,5,3', 5'-tetramethylbiadamantyl))) ethynyl) isophthalic acid, 4- ( 2- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) ethynyl) isophthalic acid, 5- (2- (7- (1,1 ′-(3 , 5,3 ', 5'-tetramethylbiadamantyl))) ethynyl) isophthalic acid, 5- (2 -(2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) ethynyl) isophthalic acid having a biadamantyl structure such as isophthalic acid and an ethynyl structure, 5- (2 -(3- (1,1'-biadamantyl)) ethynyl) terephthalic acid, 5- (2- (2- (1,1'-biadamantyl)) ethynyl) terephthalic acid, 5- (2- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) ethynyl) terephthalic acid, 5- (2- (2- (1,1 ′-(3,5,3 ′) , 5'-tetramethylbiadamantyl))) ethynyl) terephthalic acid having a biadamantyl structure and ethynyl structure such as terephthalic acid, 3- (2- (4- (1-adamantyl) phenyl) ethynyl) phthalic acid, 3 -(2- (4- (2-adamantyl) phenyl Ethynyl) phthalic acid, 4- (2- (4- (1-adamantyl) phenyl) ethynyl) phthalic acid, 4- (2- (4- (2-adamantyl) phenyl) ethynyl) phthalic acid, 3- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) phthalic acid, 3- (2- (4- (2- (1,3-dimethyladamantyl)) phenyl) ethynyl) phthalic acid, 4 -(2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) phthalic acid, 4- (2- (4- (2- (1,3-dimethyladamantyl)) phenyl) ethynyl) Phthalic acid, 3- (2- (4- (4- (1-adamantyl) phenoxy) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) Phthalic acid, 4 -(2- (4- (4- (1-adamantyl) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) phthalic acid, 3 -(2- (4- (4- (1- (3,5-dimethyladamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (2- (1,3- Dimethyladamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (1- (3,5-dimethyladamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- Phthalic acid having an adamantyl structure such as (4- (4- (2- (1,3-dimethyladamantyl)) phenoxy) phenyl) ethynyl) phthalic acid and a phenylethynyl structure, 4- (2- (4- ( 1 Adamantyl) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (2-adamantyl) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (1-adamantyl) phenyl) ethynyl) isophthalic acid, 5 -(2- (4- (2-adamantyl) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid, 4- (2 -(4- (2- (1,3-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (2- (1,3-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (1-adamantyl) fe) Xyl) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (1-adamantyl)) Phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (1- (3 , 5-dimethyladamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (2- (1,3-dimethyladamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (1- (3,5-dimethyladamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (2- (1,3- Isophthalic acid having adamantyl structure and phenylethynyl structure such as dimethyladamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (1-adamantyl) phenyl) ethynyl) terephthalic acid, 5- (2 -(4- (2-adamantyl) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) terephthalic acid, 5- (2- (4 -(2- (1,3-dimethyladamantyl)) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (1-adamantyl) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (1- (3 Adamantyl structures such as -dimethyladamantyl)) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (2- (1,3-dimethyladamantyl)) phenoxy) phenyl) ethynyl) terephthalic acid Terephthalic acid having a phenylethynyl structure, 3- (2- (4- (1-diamantyl) phenyl) ethynyl) phthalic acid, 3- (2- (4- (2-diamantyl) phenyl) ethynyl) phthalic acid, 4 -(2- (4- (1-diamantyl) phenyl) ethynyl) phthalic acid, 4- (2- (4- (2-diamantyl) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (1-diamantyl) phenoxy) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (2-diamantyl) phenoxy) phenyl) ethini ) Phthalic acid, 4- (2- (4- (4- (1-diamantyl) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (2-diamantyl) phenoxy) phenyl) ethynyl ) Phthalic acid having a diamantyl structure such as phthalic acid and a phenylethynyl structure, 4- (2- (4- (1-diamantyl) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (2-diamantyl)) Phenyl) ethynyl) isophthalic acid, 5- (2- (4- (1-diamantyl) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (2-diamantyl) phenyl) ethynyl) isophthalic acid, 4- ( 2- (4- (4- (1-diamantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (2-diamantyl) phenoxy) f Enyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (1-diamantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (2-diamantyl) phenoxy) Phenyl) ethynyl) isophthalic acid having a diamantyl structure and a phenylethynyl structure, such as isophthalic acid,
5- (2- (4- (1-diamantyl) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (2-diamantyl) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4 -(1-diamantyl) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (2-diamantyl) phenoxy) phenyl) ethynyl) terephthalic acid and the like have a diamantyl structure and a phenylethynyl structure. Terephthalic acid, 3- (2- (4- (1-tetramantyl) phenyl) ethynyl) phthalic acid, 3- (2- (4- (2-tetramantyl) phenyl) ethynyl) phthalic acid, 4- (2- (4 -(1-tetramantyl) phenyl) ethynyl) phthalic acid, 4- (2- (4- (2-tetramantyl) phenyl) ethynyl) phthalic acid, 3- (2- ( -(4- (1-tetramantyl) phenoxy) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4 Tetramantyl and phenylethynyl structures such as-(4- (1-tetramantyl) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl) phthalic acid 4- (2- (4- (1-tetramantyl) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (2-tetramantyl) phenyl) ethynyl) isophthalic acid, 5- (2 -(4- (1-tetramantyl) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (2-tetramantyl) phenyl) ethini ) Isophthalic acid, 4- (2- (4- (4- (1-tetramantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl ) Isophthalic acid, 5- (2- (4- (4- (1-tetramantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl ) Isophthalic acid having a tetramantyl structure such as isophthalic acid and a phenylethynyl structure, 5- (2- (4- (1-tetramantyl) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (2-tetramantyl)) Phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (1-tetramantyl) phenoxy) phenyl) ethynyl) te Terephthalic acid having a tetramantyl structure such as 5- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl) terephthalic acid) and a phenylethynyl structure, 3- (2- (4- ( 3- (1,1′-biadamantyl)) phenyl) ethynyl) phthalic acid, 3- (2- (4- (2- (1,1′-biadamantyl)) phenyl) ethynyl) phthalic acid, 4- ( 2- (4- (3- (1,1′-biadamantyl)) phenyl) ethynyl) phthalic acid, 4- (2- (4- (2- (1,1′-biadamantyl)) phenyl) ethynyl) Phthalic acid, 3- (2- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) phthalic acid, 3- (2- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetrame Tilbiadamantyl))) phenyl) ethynyl) phthalic acid, 4- (2- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) Ethynyl) phthalic acid, 4- (2- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) phthalic acid, 3- ( 2- (4- (4- (3- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (2- (1,1′-) Biadamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (3- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2 -(4- (4- (2- (1,1'-biadamantyl)) phenoxy) phenyl) ethynyl) Phthalic acid, 3- (2- (4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) phthalic acid, 4- ( 2- (4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- ( 4- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) phthalamyl structures such as phthalic acid and phenylethynyl structures 4- (2- (4- (3- (1,1′-biadamantyl)) phenyl) ethyl Nyl) isophthalic acid, 4- (2- (4- (2- (1,1′-biadamantyl)) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (3- (1,1′-)) Biadamantyl)) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (2- (1,1′-biadamantyl)) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (2- (1,1 ′-(3 , 5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (7- (1,1 ′-(3,5,3 ′, 5 ′) -Tetramethylbiadamantyl))) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (2- (1,1 '-(3, 5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (3- (1,1′-biadamantyl)) phenoxy) phenyl) Ethynyl) isophthalic acid, 4- (2- (4- (4- (2- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- ( 3- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (2- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl ) Isophthalic acid, 4- (2- (4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) isophthalic acid , 4- (2- (4- (4- (2- (1,1 ′-( 3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (7- (1,1 ′-(3,5) , 3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (2- (1,1 ′-(3,5,3 ′) , 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) isophthalic acid having a biadamantyl structure such as isophthalic acid and a phenylethynyl structure, 5- (2- (4- (3- (1,1 ′) -Viadamantyl)) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (2- (1,1'-biadamantyl)) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (7 -(1,1 '-(3,5,3', 5'-tetramethyl) Rubiadamantyl))) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl ) Terephthalic acid, 5- (2- (4- (4- (3- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (2 -(1,1'-biadamantyl)) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (7- (1,1 '-(3,5,3', 5 ') -Tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (2- (1,1 '-(3,5,3', 5'-tetramethyl) Biadamantyl such as Biadamantyl))) phenoxy) phenyl) ethynyl) terephthalic acid Terephthalic acid. Having a Le structure and phenylethynyl structure, the adamantane structure in the group having an alicyclic structure, it is possible to choose a structure that a minimum unit of adamantane structure described above. The coupling position may be arbitrarily selected within the range included in the formula (1).
Moreover, when using the bis o-aminophenol compound which has group which has alicyclic structure, what does not have group which has alicyclic structure in these dicarboxylic acid compounds can be used. Examples of the dicambouronic acid compound having no group having an alicyclic structure include 9,9-biscarboxyphenylfluorene, 9,9-bis [(4-carboxy-phenoxy) -phenyl] fluorene, 1,3-bis ( 4-carboxy-phenoxy) benzene, 2,2′-bis [(4-carboxy-phenoxy) -phenyl] biphenyl, and the like.
In the combination of the bis o-aminophenol compound and the dicarboxylic acid compound, in order to obtain a polybenzoxazole resin having a lower dielectric constant and excellent heat resistance, both have a group having an alicyclic structure. Is preferred.

  The dicarboxylic acid compound having an adamantane structure and a fluorene structure can be synthesized, for example, by the following method. First, Suzuki coupling reaction between 2-bromo-5- (1-adamantyl) -toluene or 1-bromo-3,5-dimethyladamantane and 4- (1-adamantyl) -benzeneboronic acid, followed by fluorene reaction The corresponding 2,7-diadamantylfluorenone or 2,7-di (3,5-dimethyl-1-adamantyl) fluorenone is synthesized by fluorenonation reaction and has an adamantyl group by dehydration reaction with methyl benzoate Obtain full orange dimethyl benzoate. 9,9-bis (4-carboxy-phenyl) -2,7-diadamantyl-fluorene can be synthesized by alkali hydrolysis and acid treatment. In addition, fluorene bisphenol having an adamantyl group, which is an intermediate reaction product of the synthesis of a bisaminophenol compound, is etherified with 4-fluoro-methyl benzoate, and further subjected to 9,9-bis [ (4-Carboxy-phenoxy) -phenyl] -2,7-diadamantyl-fluorene, 9,9-bis [(4-carboxy-phenoxy) -phenyl] -2,7-di (3,5-dimethyl-1 -Adamantyl) -fluorene can be synthesized.

  The dicarboxylic acid compound having an adamantane structure and a benzene structure can be synthesized, for example, by the following method. First, dihydroxybenzene having an adamantane structure is synthesized by a reaction between resorcinol and 1-bromoadamantane or 1-bromo-3,5-dimethyladamantane. This was etherified with methyl 4-fluoro-benzoate and further subjected to alkaline hydrolysis and acid treatment to give 1,3-bis (4-carboxyl-phenoxy) -4,6-diadamantyl-benzene, 1,3. -Bis (4-carboxyl-phenoxy) -4,6-di (3,5-dimethyl-1-adamantyl) -benzene can be synthesized.

The dicarboxylic acid compound having an adamantane structure and a biphenyl structure can be synthesized, for example, by the following method. First, dihydroxy-biphenyl having an adamantyl group is synthesized from the reaction of 2,2′-dihydroxy-biphenyl and 1-bromo-adamantane or 1-bromo-3,5-dimethyladamantane. This was etherified with methyl 4-fluoro-benzoate and further subjected to alkaline hydrolysis and acid treatment to give 2,2′-bis (4-carboxy-phenoxy) -5,5′-diadamantyl-biphenyl, 2 , 2′-bis (4-carboxy-phenoxy) -5,5′-di (3,5-dimethyl-1-adamantyl) -biphenyl can be synthesized.
In these syntheses, a bis o-aminophenol compound and dicarboxylic acid other than the above bis o-aminophenol compound and dicarboxylic acid compound may be used for copolymerization or blending.
Further, as the dicarboxylic acid compound other than the above, adamantane dicarboxylic acid, biadamantanedicarboxylic acid, tetraadamantanedicarboxylic acid, or the like may be used. Further, the group having the adamantane structure is bonded to an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a fluoroalkyl group such as a fluoromethyl group, a fluoroethyl group, a fluoropropyl group and a fluorobutyl group. It may be. Thereby, the solubility to a solvent and heat resistance can be improved further.

The method for producing the polybenzoxazole resin precursor will be described in more detail.
The polybenzoxazole resin precursor having an adamantane structure can be obtained by a reaction between the bisaminophenol compound having the adamantane structure and the dicarboxylic acid compound having the adamantane structure. The chloride method can be mentioned. Specifically, the dicarboxylic acid and an excess amount of thionyl chloride are reacted at room temperature to about 130 ° C. in the presence of a catalyst such as N, N′-dimethylformamide, and the excess thionyl chloride is heated and reduced in pressure. After leaving, the residue is recrystallized with a solvent such as hexane to obtain dicarboxylic acid chloride.
Next, the dicarboxylic acid chloride and the bisaminophenol compound are dissolved in a polar solvent such as N-methyl-2-pyrrolidone or N, N′-dimethylacetamide, and in the presence of an acid acceptor such as pyridine, A polybenzoxazole resin precursor having an adamantane structure can be obtained by reacting at about −30 ° C. to room temperature. The number of repeating units of the precursor is not particularly limited, but is preferably 2 to 1,000, and particularly preferably 5 to 100. When the number of repeating units is within the above range, the solubility and workability are particularly excellent.
Further, an active ester method may be used instead of the acid chloride method. In the active ester method, for example, a benzotriazyl ester is produced by reacting the dicarboxylic acid chloride with 1-hydroxybenzotriazole, and the ester compound and the bisaminophenol compound are heated at room temperature or higher as described above. What is necessary is just to make it react at temperature.
Further, a monofunctional carboxylic acid compound or an o-aminophenol compound may be reacted with the terminal of the resin precursor. Thereby, the solubility to a solvent and heat resistance can be improved further.
Examples of the monofunctional carboxylic acid compound include benzoyl chloride and 4-adamantyl benzoic acid chloride. Examples of the o-aminophenol compound include 2-aminophenol and 4-adamantyl-2-aminophenol.

In the present invention, examples of the method for dehydrating and cyclizing the compound having the structure represented by the general formula (1) include a heating method, active energy rays such as microwaves, visible light, UV light, and X-rays, and electrons. The method of irradiating actinic radiation, such as a line | wire, etc. is mentioned, However, Below, the method of ring-closing the said polyimide resin precursor and a polybenzoxazole resin precursor is demonstrated.
In the present invention, the polyimide resin is obtained by subjecting the polyimide resin precursor as described above to a dehydration ring-closing reaction. For example, a method of reacting at 150 to 300 ° C. × 5 (minutes) to 24 (hours), a method of irradiating UV light, a method of irradiating an electron beam, and the like can be mentioned.
In the present invention, the polybenzoxazole resin is obtained by a dehydration ring-closing reaction of the polybenzoxazole resin precursor as described above. For example, a method of reacting at 150 to 425 ° C. × 5 (minutes) to 24 (hours), a method of irradiating UV light, a method of irradiating an electron beam, and the like can be mentioned.

  As a method for producing the polyphenylene ether, for example, it can be obtained by reacting a bisphenol compound and an aromatic compound having a difluoro group under basic conditions.

  As a method for producing the polyester, for example, it can be obtained by reacting a bisphenol compound and a dicarboxylic acid compound by an acid chloride method or an active ester method.

Examples of the bisphenol compound include 9,9-bis (4-hydroxy-phenyl) -2,7-diadamantyl-fluorene and 9,9-bis [(3-hydroxy-phenoxy) -phenyl] -2,7. -Bisphenol compounds having an adamantane structure such as diadamantyl-fluorene and fluorene structures, and bisphenols having an adamantane structure such as 1,3-bis (3-hydroxy-phenoxy) -4,6-diadamantyl-benzene and a benzene structure Compounds, bisphenol compounds having an adamantane structure and a naphthalene structure, bisphenol compounds having an adamantane structure and an anthracene structure, 2,2'-dihydroxy-5,5'-diadamantyl-biphenyl and 2,2'-bis (3- Hydroxy-phenoxy) 5,5'-diadamantyl - bisphenol compound having an adamantane structure and a biphenyl structure such as biphenyl. Examples of the adamantane structure may be selected structure to the minimum unit of adamantane structure described above. The bonding position of the adamantane structure may be arbitrarily selected within the range included in the general formula (1).
As the dicarboxylic acid compound, the same dicarboxylic acid as that in the polybenzoxazole resin precursor can be selected.

  Examples of the aromatic compound having a difluoro group include 9,9-bis (4-fluoro-phenyl) -2,7-diadamantyl-fluorene and 9,9-bis [(3-fluoro-phenoxy) -phenyl]. Difluoro compounds having an adamantane structure and a fluorene structure such as −2,7-diadamantyl-fluorene, and an adamantane structure and a benzene structure such as 1,3-bis (3-fluoro-phenoxy) -4,6-diadamantyl-benzene A difluoro compound having an adamantane structure and a naphthalene structure, a difluoro compound having an adamantane structure and an anthracene structure, 2,2′-difluoro-5,5′-diadamantyl-biphenyl and 2,2′- Bis (3-fluoro-phenoxy) -5,5′- Adamantyl - difluoro compounds such as mentioned with the adamantane structure and a biphenyl structure such as biphenyl, the adamantane structure may be selected structure to the minimum unit of adamantane structure described above. The bonding position of the adamantane structure may be arbitrarily selected within the range included in the general formula (1).

In the structure represented by the general formula (1), a functional group having an acetylene bond, a biphenylene group, a cyanato group, a maleimide group, a nadiimide group, a vinyl group, a cyclopentadienyl group, etc. It may be attached to a chain. Moreover, you may copolymerize with the monomer which has these functional groups, and it can also make it blend with the polymer which has these functional groups. Thereby, the solubility to a solvent and heat resistance can be improved further.
In the monomer having the functional group, for example, as a monomer having a functional group having an acetylene bond, examples of the dicarboxylic acid compound having an acetylene bond include 5-phenylethynylisophthalic acid, 5- (4-phenylethynyl-phenoxy) -isophthalate. Acid, 5-ethynylisophthalic acid, 5- (4-ethynyl-phenoxy) -isophthalic acid, 5-adamantylethynyl-isophthalic acid and 5-phenylethynyl-adamantane-1,3-dicarboxylic acid. As the bisaminophenol compound having an acetylene bond, 2,7-bisphenylethynyl-9,9-bis (4-hydroxy-3-amino-phenyl) -fluorene, 2,7-diethynyl-9,9- Bis (4-hydroxy-3-amino-phenyl) -fluorene, 2,7-bisphenylethynyl-9,9-bis [4- (3-hydroxy-4-amino-phenoxy) -phenyl] -fluorene and 2, 7-diethynyl-9,9-bis [4- (3-hydroxy-4-amino-phenoxy) -phenyl] -fluorene and the like.

In addition to the above components, the resin composition of the present invention includes a surfactant, a coupling agent typified by a silane, a radical initiator that generates oxygen radicals and sulfur radicals upon heating, and disulfides, as necessary. Additives such as catalysts can be used.
Moreover, the said resin composition can also be used as a photosensitive resin composition by adding the naphthoquinone diazide compound etc. as a photosensitive agent to the said resin composition. For example, as a specific example, a hydroxyl group is introduced into the resin composition, or when any _one of R _{1 to} R ₁₀ in the general formula (1) is a hydroxyl group, that is, a polybenzoxazole resin precursor. Can be used together with a naphthoquinone diazide compound as a photosensitizer so that the resin composition can be used as a positive photosensitive resin composition. Further, when the resin composition has a group containing a photocrosslinkable group such as a methacryloyl group, it is possible to use the resin composition as a negative photosensitive resin composition by using a photoinitiator. .
The resin composition of the present invention can be obtained by appropriately blending the above components and mixing them.

  The resin composition of the present invention is preferably used in the production of a resin film or the like as a varnish by dissolving or dispersing the resin film or the like in an organic solvent capable of dissolving or dispersing the resin film or the like. Examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether. , Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3- Methoxypropionate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, tetrahydro Rofuran, toluene, xylene, can be mentioned mesitylene, be other than these, any organic solvent capable of dissolving or dispersing, it can be used. These organic solvents may be used alone or in combination of two or more.

  Further, the amount of the solvent to be used is not particularly limited as long as the resin composition can be completely dissolved or dispersed, and can be appropriately adjusted according to the use, but in general, the varnish The solvent content is preferably about 70 to 95% by weight.

Next, the resin film will be described.
The resin film of the present invention is obtained using the resin composition as described above. Thereby, the said resin film is excellent in adhesiveness and dimensional stability.
The resin film is, for example, a semiconductor interlayer insulating film or surface protective film, a multilayer circuit interlayer insulating film, a flexible copper-clad plate cover coat, a solder resist film, a liquid crystal alignment film, an etching protective film (etching stopper), an adhesive It can be used as an agent. Among these, it is suitably used as an interlayer insulating film for semiconductors, a surface protective film, and an etching protective film.

  Further, by adding a naphthoquinone diazide compound or the like as a photosensitizer to the resin composition, the resin composition can be used as a surface protective film having photosensitivity.

When the resin film is used as an interlayer insulating film, for example, the resin composition is dissolved in an organic solvent such as N-methyl-2-pyrrolidone to prepare a varnish, and the varnish is used as an appropriate support, for example, Then, it is applied to a silicon wafer, a ceramic substrate or the like to form a coating film. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Thereafter, the coating film is dried, subjected to heat treatment, and the solvent is removed, whereby an interlayer insulating film can be obtained. In the case of a polyimide resin precursor or a polybenzoxazole resin precursor, following the solvent removal, a condensation reaction and a cross-linking reaction are performed by a known method to obtain a polyimide resin or a polybenzoxazole resin, and a resin composition containing the same. It can be set as the comprised interlayer insulation film. In addition, if the resin converted from the polyimide resin precursor or polybenzoxazole resin precursor is soluble in an organic solvent, the varnish is converted into a polyimide resin or polybenzoxazole resin in advance. Then, an interlayer insulating film can be obtained by the same method. In that case, in the heat processing of a coating film, since the process of converting a polyimide resin precursor or a polybenzoxazole resin precursor into resin is not required, heat processing time can be shortened.
The thickness of the interlayer insulating film is not particularly limited, but is preferably 0.01 to 20 μm, particularly preferably 0.05 to 10 μm, and most preferably 0.1 to 0.7 μm. When the thickness is within the above range, process compatibility is excellent.

  Further, when the resin film is used as a protective film for the semiconductor, the resin composition is made of, for example, propylene acid, diacetone alcohol, N-methyl-2-pyrrolidone, etc. A varnish is prepared by dissolving in an organic solvent, and the varnish is applied to a suitable support such as a silicon wafer or a ceramic substrate. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Then, it can be set as a protective film by drying, heat-processing, and removing a solvent. In the case of a polyimide resin precursor or a polybenzoxazole resin precursor, after the solvent removal, a dehydration reaction may be performed to form a polyimide resin or a polybenzoxazole resin, and a protective film composed of a resin composition containing the polyimide resin or polybenzoxazole resin. it can.

  Although the thickness of the said protective film is not specifically limited, 0.05-70 micrometers is preferable and especially 0.1-50 micrometers is preferable. When the thickness is within the above range, both the protective properties and workability of the semiconductor element are particularly excellent.

Next, a semiconductor device will be described based on a preferred embodiment.
FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device of the present invention.
The semiconductor device 100 includes a semiconductor substrate 1 on which elements are formed, a silicon nitride film 2 provided on the upper side of the semiconductor substrate 1 (upper side in FIG. 1), an interlayer insulating film 3 provided on the silicon nitride film 2, and A copper wiring layer 4 covered with a barrier layer 6 is provided.
A recess corresponding to the pattern to be wired is formed in the interlayer insulating film 3, and a copper wiring layer 4 is provided in the recess.
In addition, a reforming treatment layer 5 is provided between the interlayer insulating film 3 and the copper wiring layer 4.
A hard mask layer 7 is formed on the upper side of the interlayer insulating film 3 (on the side surface opposite to the silicon nitride film 2).

  In the present embodiment, the semiconductor device 100 using the interlayer insulating film 3 has been described. However, the present invention is not limited to this.

Since the semiconductor device of the present invention uses the interlayer insulating film as described above, it is excellent in dimensional accuracy and can sufficiently exhibit insulation, thereby providing excellent connection reliability.
In addition, since the interlayer insulating film as described above has excellent adhesion to the wiring layer, the connection reliability of the semiconductor device can be further improved.
In addition, since the interlayer insulating film as described above has excellent dielectric characteristics, signal loss of the semiconductor device can be reduced.
In addition, since the interlayer insulating film as described above has excellent dielectric characteristics, wiring delay can be reduced.

(Example)
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this. In addition, the following method was used for identification of the obtained compound.
1. Mass spectrometry (MS): Measured by a field desorption (FD) method using a JMS-700 type mass spectrometer manufactured by JEOL Ltd.
2. Elemental analysis: Carbon, hydrogen and nitrogen were measured using a 2400 type elemental analyzer manufactured by PERKIN ELMER, and chlorine was measured by a flask combustion titration method.

(Synthesis Example 1)
[Synthesis of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene]
A 300 mL eggplant flask was charged with 75.0 g (349 mmol) of 1-bromoadamantane, 9.58 g (87.0 mmol) of 1,3-dihydroxybenzene, 25 mL of toluene and a stirring bar, and heated at 130 ° C. for 24 hours under a nitrogen stream. Stirring was performed. Subsequently, the solvent was removed under reduced pressure, and the obtained solid was purified by column chromatography to obtain 23.0 g (60.8 mmol; 4,0.8 mmol of 4,6-di (1-adamantyl) -1,3-dihydroxybenzene; 69.9%).

  Next, 22.0 g (58.1 mmol) of 4,6- (1-adamantyl) -1,3-dihydroxybenzene obtained above and 28.7 g of 2-benzyloxy-4-fluoronitrobenzene were placed in a 300 mL eggplant flask. (116 mmol), potassium carbonate 32.1 g (233 mmol), N, N-dimethylformamide 180 mL and a stirrer were added, and the mixture was heated and stirred at 135 ° C. for 12 hours in a nitrogen stream. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, further stirred in 1 L of ion exchange water for 1 hour, and then dried under reduced pressure, whereby 4,6-di (1-adamantyl) -1,3-bis (4-nitro -3-Benzyloxyphenoxy) benzene 40.5g (48.6mmol; Yield 83.6%) was obtained.

Next, 39.0 g (46.8 mmol) of 4,6-di (1-adamantyl) -1,3-bis (4-nitro-3-benzyloxyphenoxy) benzene obtained above was added to a 300 mL eggplant flask. 10.49 g (1.40 mmol) of 10% palladium-activated carbon, 273 mL of N, N-dimethylformamide and a stirrer were added, and the mixture was stirred at 25 ° C. for 24 hours in a hydrogen atmosphere. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, further stirred in 1 L of ion exchange water for 1 hour, and then dried under reduced pressure, whereby 4,6-di (1-adamantyl) -1,3-bis (4-amino- 34.0 g (40.5 mmol; yield 86.5%) of 3-hydroxyphenoxy) benzene was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 593 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 77.00; H, 7.48; N, 4.73; O, 10.80, Actual value (/%): C, 76.95; H, 7 .50; N, 4.71; O, 10.81

(Synthesis Example 2)
[Synthesis of 4,6-di (3,5-dimethyl-1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene]
The synthesis was performed in the same manner as in Synthesis Example 1, except that 84.8 g (349 mmol) of 1-bromo-3,5-dimethyladamantane was used instead of 75.0 g (349 mmol) of 1-bromoadamantane.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 648 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 77.74; H, 8.08; N, 4.32; O, 9.86, measured value (/%): C, 77.70; H, 8 .03; N, 4.31; O, 9.88

(Synthesis Example 3)
[Synthesis of 4,6-di (3- (1-adamantyl) -1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene]
Synthesis was performed in the same manner as in Synthesis Example 1, except that 121.9 g (349 mmol) of 3-bromo-1,1′-biadamantane was used instead of 75.0 g (349 mmol) of 1-bromoadamantane.
The results of mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
MS (FD) (m / z): 861 (M ⁺ )
Elemental analysis: Theoretical value (%): C, 80.89; H, 8.43; N, 3.25; O, 7.43,
Found (%): C, 80.83; H, 8.49; N, 3.32; O, 7.33

(Synthesis Example 4)
[4,6-di (3- (3,5-dimethyl-1-adamantyl)-(3,5-dimethyl-1-adamantyl))-1,3-bis (4-amino-3-hydroxyphenoxy) benzene Synthesis]
In Synthesis Example 1, 141 g (349 mmol) of 1-bromo-3,5-dimethyl-7- (3,5-dimethyl-1-adamantyl) adamantane was used instead of 75.0 g (349 mmol) of 1-bromoadamantane. The other components were synthesized in the same manner as in Synthesis Example 1.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 973 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 81.44; H, 9.11; N, 2.88; O, 6.57, Actual value (/%): C, 81.40; H, 9 .10; N, 2.87; O, 6.56

(Synthesis Example 5)
[Synthesis of 9,9-bis (3-amino-4-hydroxy-phenyl) -2,7-di (1-adamantyl) -fluorene]
(1) [Synthesis of 4,4′-diadamantyl-2-methyl-1,1′-biphenyl]
A 1 L three-necked flask equipped with a Dimroth condenser and a stirrer was charged with 3.19 g (0.131 mol) of magnesium, 40 g (0.131 mol) of 5-adamantyl-2-bromotoluene and 200 mL of tetrahydrofuran. The Grignard reagent was prepared by refluxing for 2 hours. Next, to a 1 L three-necked flask equipped with a Dimroth condenser and a stirrer was added 38.15 g (0.131 mol) of 1-adamantyl-4-bromobenzene, 9.19 mg (0,0) of bis (triphenylphosphine) palladium dichloride. 0.131 mmol) and 300 mL of THF were charged, and nitrogen was allowed to flow. The THF solution of the Grignard reagent prepared above was added here, and it recirculate | refluxed for 12 hours. Subsequently, 60 mL of a 10% hydrochloric acid aqueous solution was added and refluxed for 30 minutes. The reaction solution was cooled to room temperature, the organic layer was separated using a separatory funnel, and the aqueous layer was extracted twice with 50 mL of THF. The organic layers were combined, washed with 200 mL of saturated sodium bicarbonate, followed by 200 mL of water, and dried over anhydrous sodium sulfate. The solvent was distilled off with an evaporator and purified by alumina column chromatography (hexane / THF = 1: 1) to obtain 45.1 g of 4,4′-diadamantyl-2-methyl-1,1′-biphenyl. (Yield 79%).

(2) [Synthesis of 2,7-diadamantylfluorenone]
To a 500 mL autoclave, 45.1 g (0.10 mol) of 4,4′-diadamantyl-2-methyl-1,1′-biphenyl obtained above, 36.8 g (0.125 mol) of potassium dichromate, 200 mL of water was charged and heated at 250 ° C. for 48 hours. After cooling, the precipitate was filtered off, washed three times with 200 mL of ion-exchanged water, filtered again, and stirred in a pH 1 sulfuric acid aqueous solution for 2 hours. The precipitate was filtered off from the aqueous solution, washed with 200 mL of ion exchange water three times, and then with 100 mL of methanol to obtain 42.2 g of 2,7-diadamantylfluorenone (yield 94%).

(3) [Synthesis of 2,7-diadamantylfluorene-9,9-bisphenol]
In a 500 mL four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 66.4 g (0.148 mol) of 2,6-diadamantylfluorenone obtained above and 41.8 g (0.444 mol (3) of phenol were obtained. The Eaton reagent (7.7 wt% diphosphorus pentoxide in methanesulfonic acid solution) (203 mL) was added and heated at 150 ° C. for 12 hours in a nitrogen atmosphere. After the reaction solution returned to room temperature, 30 mL of ion exchange water was slowly added. The reaction solution was transferred to a separatory funnel, extracted with 20 mL of ethyl acetate three times, dried over magnesium sulfate, and then the ethyl acetate was distilled off with an evaporator. The resulting crude product was purified by column chromatography (hexane / ethyl acetate = 4/1) to obtain 74.3 g of 2,7-diadamantylfluorene-9,9-bisphenol (0. 12 mol, yield 81.1%).

Next, 200 mL (0.64 mol) of a 20% aqueous nitric acid solution was placed in a four-necked 500 mL flask equipped with a thermometer, a stirrer, and a reflux tube, and 2,7-diadamantylfluorene-9, 68.1 g (0.11 mol) of 9-bisphenol was added in small portions. During the addition, the internal temperature was kept at 20 ° C to 30 ° C. When the temperature did not rise after completion of the addition, the reaction was continued for 1 hour. Thereafter, the mixture was poured into about 500 mL of cold water, the crude product was filtered off, washed with pure water, and dried. Furthermore, the crude product was recrystallized with hot ethanol.
The obtained recrystallized product was dried under reduced pressure to obtain 71.0 g (0,9,9-bis (3-nitro-4-hydroxy-phenyl) -2,7-di (1-adamantyl) -fluorene product. .10 mol; yield 91.0%).

Next, in a 300 mL eggplant flask, 71.0 g (0.10 mol) of 9,9-bis (3-nitro-4-hydroxy-phenyl) -2,7-di (1-adamantyl) -fluorene obtained above was obtained. 0.318 g (0.30 mmol) of 10% palladium-activated carbon, 273 mL of N, N-dimethylformamide and a stirrer were added, and the mixture was stirred at 25 ° C. for 24 hours in a hydrogen atmosphere. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, and further stirred for 1 hour in 1 L of ion exchange water, and then dried under reduced pressure, whereby 9,9-bis (3-amino-4-hydroxy-phenyl) -2,7 -61.0 g (0.094 mol; yield 94.0%) of di (1-adamantyl) -fluorene was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 649 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 83.30; H, 7.46; N, 4.32; O, 4.93, measured value (/%): C, 83.36; H, 7 .35; N, 4.36; O, 4.91

(Synthesis Example 6)
[Synthesis of 9,9-bis (3-amino-4-hydroxy-phenyl) -2,7-di (3,5-dimethyl-1-adamantyl) -fluorene]
In Synthesis Example 5, Synthesis Example 5 except that 41.7 g (131 mmol) of 3,5-dimethyl-1-adamantyl-4-bromobenzene was used instead of 38.15 g (131 mmol) of 1-adamantyl-4-bromobenzene. Was synthesized in the same manner as above.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 704 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 83.48; H, 8.01; N, 3.97; O, 4.54, measured value (/%): C, 83.49; H, 8 .00; N, 3.98; O, 4.52

(Synthesis Example 7)
[Synthesis of 9,9-bis [4- (3-hydroxy-4-amino-phenoxy) -phenyl] -2,7-di (1-adamantyl) -fluorene]
In a 300 mL eggplant flask, 36.0 g (58.1 mmol) of 2,7-diadamantylfluorene-9,9-bisphenol obtained in Synthesis Example 5 and 28.7 g (116 mmol) of 2-benzyloxy-4-fluoronitrobenzene were obtained. ), Potassium carbonate 32.1 g (233 mmol), N, N-dimethylformamide 180 mL and a stirrer were added, and the mixture was heated and stirred at 135 ° C. for 12 hours under a nitrogen stream. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, further stirred in 1 L of ion exchange water for 1 hour, and then dried under reduced pressure, whereby 9,9-bis [4- (4-nitro-3-benzyloxyphenoxy)- Phenyl] -2,7-di (1-adamantyl) -fluorene (52.5 g, 48.9 mmol; yield 84.2%) was obtained.

Next, the 9,9-bis [4- (4-nitro-3-benzyloxyphenoxy) -phenyl] -2,7-di (1-adamantyl) -fluorene obtained above was placed in a 300 mL eggplant flask. 2 g (46.8 mmol), 1.49 g (1.40 mmol) of 10% palladium-activated carbon, 273 mL of N, N-dimethylformamide and a stirrer were added, and the mixture was stirred at 25 ° C. for 24 hours in a hydrogen atmosphere. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, further stirred in 1 L of ion exchange water for 1 hour, and then dried under reduced pressure, whereby 9,9-bis [4- (3-hydroxy-4-amino-phenoxy)- Phenyl] -2,7-di (1-adamantyl) -fluorene 34.6 g (41.5 mmol; yield 88.7%) was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 1041 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 84.20; H, 6.97; N, 2.69; O, 6.15, Measured value (/%): C, 84.17; H, 6 .95; N, 2.70; O, 6.13

(Synthesis Example 8)
[Synthesis of 2,2′-dihydroxy-3,3′-diamino-5,5′-bis [3- (1-adamantyl)-(1-adamantyl)]-biphenyl]
A 3-L eggplant-shaped flask was charged with 1210.9 g (3.9 mol) of 3-bromo-1,1′-biadamantane, 162.0 g (870.0 mmol) of 2,2′-dihydroxy-biphenyl, 250 mL of toluene, and a stirring bar. The mixture was heated and stirred at 130 ° C. for 24 hours under a nitrogen stream. Subsequently, the solvent was removed under reduced pressure, and the obtained solid was purified by column chromatography to obtain 2,2′-dihydroxy-5,5′-bis [3- (1-adamantyl)-(1-adamantyl) ] -Biphenyl 428.1g (592.0mmol; Yield 68.0%) was obtained.

Next, 200 mL (0.64 mol) of a 20% nitric acid aqueous solution was put into a four-necked 500 mL flask equipped with a thermometer, a stirrer, and a reflux tube, and 2,2′-dihydroxy-5,5 was stirred vigorously. '-Bis [3- (1-adamantyl)-(1-adamantyl)]-biphenyl 216.9 g (0.30 mol) was added in small portions. During the addition, the internal temperature was kept at 20 ° C to 30 ° C. When the temperature did not rise after completion of the addition, the reaction was continued for 1 hour. Thereafter, the mixture was poured into about 500 mL of cold water, the crude product was filtered off, washed with pure water, and dried. Furthermore, the crude product was recrystallized with hot ethanol.
The obtained recrystallized product was dried under reduced pressure to give 2,2′-dihydroxy-3,3′-dinitro-5,5′-bis [3- (1-adamantyl)-(1-adamantyl)]- 207.3 g (0.255 mol; yield 85.0%) of biphenyl was obtained.

Next, the 2,2′-dihydroxy-3,3′-dinitro-5,5′-bis [3- (1-adamantyl)-(1-adamantyl)]-biphenyl obtained above was added to a 300 mL eggplant flask. 81.3 g (0.10 mol), 10% palladium-activated carbon 0.318 g (0.30 mmol), N, N-dimethylformamide 273 mL and a stirrer were added, and the mixture was stirred at 25 ° C. for 24 hours in a hydrogen atmosphere. . After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, further stirred in 1 L of ion exchange water for 1 hour, and then dried under reduced pressure, whereby 2,2′-dihydroxy-3,3′-diamino-5,5′-bis. 69.3 g (0.092 mol; yield 92.0%) of [3- (1-adamantyl)-(1-adamantyl)]-biphenyl was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 753 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 82.93; H, 9.10; N, 3.72; O, 4.25, measured value (/%): C, 82.92; H, 9 .15; N, 3.66; O, 4.27

(Synthesis Example 9)
[Synthesis of 2,2′-dihydroxy-3,3′-diamino-5,5′-bis (3,5-dimethyl-1-adamantyl) -biphenyl]
Synthesis Example 8 is the same as Synthesis Example 8 except that 141 g (349 mmol) of 1-bromo-3,5-dimethyladamantane was used instead of 1210.9 g (3.9 mol) of 3-bromo-1,1′-biadamantane. It synthesized similarly.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 540 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 79.96; H, 8.95; N, 5.18; O, 5.92, Actual value (/%): C, 79.98; H, 8 .94; N, 5.17; O, 5.93

(Synthesis Example 10)
Of [2,2′-dihydroxy-3,3′-diamino-5,5′-bis (3- (5,7-dimethyl-1-adamantyl)-(3,5-dimethyl-1-adamantyl)) biphenyl Composition]
In Synthesis Example 8, instead of 1210.9 g (3.9 mol) of 3-bromo-1,1′-biadamantane, 3-bromo-5,5′-7,7′-tetramethyl-1,1′-bi Synthesis was performed in the same manner as in Synthesis Example 8 except that 141 g (349 mmol) of adamantane was used.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 865 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 83.28; H, 9.78; N, 3.24; O, 3.70, measured value (/%): C, 83.26; H, 9 .78; N, 3.25; O, 3.71

(Synthesis Example 11)
[2,2′-bis [4- (3-hydroxy-4-amino) phenoxy] -5,5′-bis [(synthesis of (3- (1-adamantyl)-(1-adamantyl))-biphenyl]
In a 300 mL eggplant flask, 42.0 g (58.2-dihydroxy-5,5′-bis [3- (1-adamantyl)-(1-adamantyl)]-biphenyl obtained in Synthesis Example 8 was obtained. 1 mmol), 28.7 g (116 mmol) of 2-benzyloxy-4-fluoronitrobenzene, 32.1 g (233 mmol) of potassium carbonate, 180 mL of N, N-dimethylformamide and a stirrer, and the mixture was stirred at 135 ° C. under a nitrogen stream at 12O 0 C. Stirring was performed for hours. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, and further stirred for 1 hour in 1 L of ion exchange water, and then dried under reduced pressure, whereby 2,2′-bis [4- (3-benzyloxy-4-nitro-phenoxy) was dried. -Phenyl] -5,5′-bis [3- (1-adamantyl)-(1-adamantyl)]-biphenyl 57.9 g (49.2 mmol; yield 84.8%) was obtained.

Next, the 2,2′-bis [4- (3-benzyloxy-4-nitro-phenoxy) -phenyl] -5,5′-bis [3- (1-adamantyl) obtained above was added to a 300 mL eggplant flask. )-(1-adamantyl)]-biphenyl 55.1 g (46.8 mmol), 10% palladium-activated carbon 1.49 g (1.40 mmol), N, N-dimethylformamide 273 mL and a stirrer were charged under hydrogen atmosphere. And stirring at 25 ° C. for 24 hours. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, and further stirred for 1 hour in 1 L of ion exchange water, and then dried under reduced pressure, whereby 2,2′-bis [4- (3-hydroxy-4-amino-phenoxy). ] -5,5′-bis [3- (1-adamantyl)-(1-adamantyl)]-biphenyl 39.0 g (41.6 mmol; yield 88.8%) was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 937 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 82.01; H, 8.17; N, 2.99; O, 6.83, Measured value (/%): C, 82.00; H, 8 .12; N, 3.02; O, 6.86

(Synthesis Example 12)
[2,2′-bis [4- (3-hydroxy-4-amino) phenoxy] -5,5′-bis (synthesis of 3- (3,5-dimethyl-1-adamantyl) biphenyl]
In Synthesis Example 8, 2,2 ′ obtained by using 141 g (349 mmol) of 1-bromo-3,5-dimethyladamantane instead of 1210.9 g (3.9 mol) of 3-bromo-1,1′-biadamantane -Dihydroxy-5,5'-bis (3,5-dimethyl-1-adamantyl) -biphenyl 29.6 g (58.1 mmol) was synthesized in Synthesis Example 11 with 2,2'-dihydroxy-5,5'-bis [ Synthesis was performed in the same manner as in Synthesis Example 11 except that 4- (1-adamantyl)-(1-adamantyl)]-biphenyl was used instead of 42.0 g (58.1 mmol).
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 724 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 79.52; H, 7.79; N, 3.86; O, 8.83, Actual value (/%): C, 79.50; H, 7 .80; N, 3.84; O, 8.81

(Synthesis Example 13)
[Synthesis of 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dichloride]
In a 500 mL four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 46.2 g of 4,6-di (1-adamantyl) -1,3-dihydroxybenzene obtained in Synthesis Example 1 ( 0.122 mol), 38.8 g (0.252 mol) of methyl 4-fluorobenzoate, and 300 mL of N, N-dimethylformamide were added, and 42.1 g (0.304 mol) of potassium carbonate was further added. After stirring at 135 ° C. for 12 hours, the reaction solution was filtered. The filtrate was added dropwise to 2000 mL of ion exchange water. The precipitated solid was washed twice with 2000 mL of methanol and dried under reduced pressure at 50 ° C. for 2 days to give 4,6-di (1-adamantyl) -1,3-bis (4-carboxymethyl-phenoxy) benzene 64. 0.6 g (0.105 mol, yield 86.1%) was obtained.

[Synthesis of 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dipotassium salt]
1 L of n-butanol and 65.9 g (1.0 mol) of potassium hydroxide (85%) were charged in a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, and dissolved by heating under reflux. To this, 61.5 g (0.10 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-carboxymethyl-phenoxy) benzene obtained by repeating the above operation was added for 30 minutes. Heated to reflux. This was cooled in an ice bath, and the precipitated crystals were collected by filtration. The crystals were washed twice with 1 L of ethanol and dried under reduced pressure at 60 ° C., whereby 66.0 g of 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dipotassium salt. (0.095 mol, yield 95.0%) was obtained.

Into a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dipotassium obtained above 62.5 g (0.09 mol) of salt and 200 mL of 1,2-dichloroethane were charged and cooled to 0 ° C. To this, 178.5 g (1.5 mol) of thionyl chloride was added dropwise at 5 ° C. or less over 1 hour. Thereafter, 1.5 mL of dimethylformamide and 1.5 g of hydroquinone were added, followed by stirring at 45 to 50 ° C. for 3 hours. After cooling, the crystals were removed by filtration, and the crystals were washed with 50 mL of chloroform. The filtrate and the washing solution were combined and concentrated under reduced pressure at 40 ° C. or lower, and the resulting residue was extracted and filtered twice with 200 mL of diethyl ether. Diethyl ether was distilled off from the extract under reduced pressure to obtain a semisolid crude product. This was washed with dry n-hexane and subsequently recrystallized with diethyl ether to give 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene-2. 38.9 g (0.0594 mol, yield 66.0%) of chloride was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Pale yellow solid MS (FD) (m / z): 656 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 73.28; H, 6.15; Cl, 10.81; O, 9.76, measured value (/%): C, 73.25; H, 6 .21; Cl, 10.75; O, 9.79

(Synthesis Example 14)
[Synthesis of 4,6-di (3,5-dimethyl-1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dichloride]
In Synthesis Example 13, 4,6-di (3,5-dimethyl-1-adamantyl) was used instead of 46.2 g (0.122 mol) of 4,6-di (1-adamantyl) -1,3-dihydroxybenzene. Synthesis was performed in the same manner as in Synthesis Example 13 except that 53.0 g (0.122 mol) of 1,3-dihydroxybenzene was used.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 711 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 74.25; H, 6.80; Cl, 9.96; O, 8.99, measured value (/%): C, 74.23; H, 6 .81; Cl, 9.98; O, 8.96

(Synthesis Example 15)
[Synthesis of 4,6-di [(3- (1-adamantyl)-(1-adamantyl))-1,3-bis (4-carboxy-phenoxy) benzene dichloride]
A 300 mL eggplant flask was charged with 121.9 g (349 mmol) of 3-bromo-1,1′-biadamantane, 9.58 g (87.0 mmol) of 1,3-dihydroxybenzene, 25 mL of toluene and a stirrer, and under a nitrogen stream. The mixture was heated and stirred at 130 ° C. for 24 hours. Subsequently, the solvent was removed under reduced pressure, and the obtained solid was purified by column chromatography to obtain 4,6-di [3- (1-adamantyl)-(1-adamantyl)]-1,3-dihydroxy. 37.4 g (57.8 mmol; yield 66.4%) of benzene was obtained.
Next, in Synthesis Example 13, instead of 46.2 g (0.122 mol) of 4,6-di (1-adamantyl) -1,3-dihydroxybenzene, 4,6-di [3- Synthesis was performed in the same manner as in Synthesis Example 13 except that 78.9 g (0.122 mol) of (1-adamantyl)-(1-adamantyl)]-1,3-dihydroxybenzene was used, and 4,6-di [( 3- (1-adamantyl)-(1-adamantyl))-1,3-bis (4-carboxy-phenoxy) benzene dichloride was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: pale yellow solid MS (FD) (m / z): 924 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 77.98; H, 7.42; Cl, 7.67; O, 6.93, Actual value (/%): C, 78.02; H, 7 .46; Cl, 7.62; O, 6.90

(Synthesis Example 16)
[4,6-di [(3- (5,7-dimethyl-1-adamantyl)-(3,5-dimethyl-1-adamantyl))-1,3-bis (4-carboxy-phenoxy) benzene dichloride Synthesis]
In Synthesis Example 13, instead of 46.2 g (0.122 mol) of 4,6-di (1-adamantyl) -1,3-dihydroxybenzene, 4,6-di [(3- (5,7-dimethyl-1- Synthesis was performed in the same manner as in Synthesis Example 13 except that 92.6 g (0.122 mol) of adamantyl)-(3,5-dimethyl-1-adamantyl))-1,3-dihydroxybenzene was used.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 1036 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 78.81; H, 8.17; Cl, 6.84; O, 6.18, Actual value (/%): C, 78.79; H, 8 .20; Cl, 6.82; O, 6.19

(Synthesis Example 17)
[Synthesis of 2,7-diadamantylfluorene-9,9-bisbenzoic acid dichloride]
In a 500 mL four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, 44.9 g (100 mmol) of 2,7-diadamantylfluorenone obtained in Synthesis Example 5 and 36.6 g (300 mmol) of benzoic acid were obtained. Was added, and 203 mL of Eaton's reagent (7.7 wt% diphosphorus pentoxide in methanesulfonic acid) was added and heated at 150 ° C. for 12 hours in a nitrogen atmosphere. After the reaction solution returned to room temperature, 100 mL of ion exchange water was slowly added. The reaction solution was transferred to a separatory funnel, extracted with 100 mL of ethyl acetate three times, dried over magnesium sulfate, and then the ethyl acetate was distilled off with an evaporator. The obtained crude product was purified by column chromatography (hexane / ethyl acetate = 4/1) to obtain 54.7 g of 2,7-diadamantylfluorene-9,9-bisbenzoic acid (81 mmol). Yield 81%).

Next, 54.7 g (81 mmol) of 2,7-diadamantylfluorene-9,9-bisbenzoic acid obtained by the above method was added to a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer. 1,2-dichloroethane 200 mL was charged and cooled to 0 ° C. To this, 178.5 g (1.5 mol) of thionyl chloride was added dropwise at 5 ° C. or less over 1 hour. Thereafter, 1.5 mL of dimethylformamide and 1.5 g of hydroquinone were added, followed by stirring at 45 to 50 ° C. for 3 hours. After cooling, the crystals were removed by filtration, and the crystals were washed with 50 mL of chloroform. The filtrate and the washing solution were combined and concentrated under reduced pressure at 40 ° C. or lower, and the resulting residue was extracted and filtered twice with 200 mL of diethyl ether. Diethyl ether was distilled off from the extract under reduced pressure to obtain a semisolid crude product. This was washed with dry n-hexane and subsequently recrystallized with diethyl ether to give 39.4 g (55 of 2,7-di (1-adamantyl) fluorene-9,9-bisbenzoic acid dichloride (55 0.4 mmol, yield 68.4%).
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: pale yellow solid MS (FD) (m / z): 712 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 79.31; H, 6.23; Cl, 9.96; O, 4.50, measured value (/%): C, 79.34; H, 6 .26; Cl, 9.87; O, 4.53

(Synthesis Example 18)
[Synthesis of 2,7-di (3,5-dimethyl-1-adamantyl) fluorene-9,9-bisbenzoic acid dichloride]
In Synthesis Example 17, synthesis was conducted except that 50.4 g (100 mmol) of 2,7-di (3,5-dimethyl-1-adamantyl) fluorenone was used instead of 44.9 g (100 mmol) of 2,7-diadamantylfluorenone. Performed as in Example 17.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 767 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 79.77; H, 6.83; Cl, 9.23; O, 4.17, measured value (/%): C, 79.75; H, 6 .80; Cl, 9.21; O, 4.16

(Synthesis Example 19)
[Synthesis of 9,9-bis [4- (4-carboxy-phenoxy) -phenyl] -2,7-di (1-adamantyl) -fluorene dichloride]
Instead of 4,6.2-di (1-adamantyl) -1,3-dihydroxybenzene (46.2 g, 0.122 mol) in Synthesis Example 13, 2,7-di (1- This was carried out in the same manner as in Synthesis Example 13 except that 75.5 g of adamantyl) fluorene-9,9-bisphenol was used.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: pale yellow solid MS (FD) (m / z): 896 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 79.09; H, 5.85; Cl, 7.91; O, 7.14, Actual value (/%): C, 79.14; H, 5 89; Cl, 7.87; O, 7.10

(Synthesis Example 20)
[Synthesis of 9,9-bis [4- (4-carboxy-phenoxy) -phenyl] -2,7-di (3,5-dimethyl-1-adamantyl) -fluorene dichloride]
Instead of 46.2 g (0.122 mol) of 4,6-di (1-adamantyl) -1,3-dihydroxybenzene in Synthesis Example 13, 2,7-di (3,5-dimethyl-1-adamantyl) fluorene This was carried out in the same manner as in Synthesis Example 13, except that 82 g (0.122 mol) of -9,9-bisphenol was used.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: pale yellow solid MS (FD) (m / z): 952 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 79.48; H, 6.35; Cl, 7.45; O, 6.72, measured value (/%): C, 79.46; H, 6 .32; Cl, 7.42; O, 6.73

(Synthesis Example 21)
[Synthesis of 2,2′-bis [(4-carboxy-phenoxy) -phenyl] -5,5′-bis [3- (1-adamantyl)-(1-adamantyl)]-biphenyl dichloride]
Instead of 4,6.2-di (1-adamantyl) -1,3-dihydroxybenzene (46.2 g, 0.122 mol) in Synthesis Example 13, 2,2′-dihydroxy-5,5 obtained in Synthesis Example 8 This was carried out in the same manner as in Synthesis Example 13 except that 88.2 g (0.122 mol) of '-bis [3- (1-adamantyl)-(1-adamantyl)]-biphenyl was used.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Light yellow solid MS (FD) (m / z): 1,000 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 79.26; H, 7.26; Cl, 7.09; O, 6.40, measured value (/%): C, 79.23; H, 7 .29; Cl, 7.12; O, 6.36

(Synthesis Example 22)
[Synthesis of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dichloride from 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt]
(1) [Synthesis of 1-ethynyladamantane]
According to the method described in the literature (Y. Okano, T. Masuda and T. Higashira, Journal of Polymer Science: Polymer Chemistry Edition, Vol. 23, 2527-2537, 1985) Synthesized.
(2) [Synthesis of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne from dimethyl 5-bromo-isophthalate]
In a 1 L four-necked flask equipped with a thermometer, a Dimroth condenser, a nitrogen inlet tube and a stirrer, 125 g (0.458 mol) of dimethyl 5-bromo-isophthalate, 1.1 g (0.00419 mol) of triphenylphosphine, iodine 0.275 g (0.00144 mol) of copper chloride and 64.26 g (0.401 mol) of 1-ethynyladamantane obtained above were charged, and nitrogen was allowed to flow into the flask. Subsequently, 375 mL of dehydrated triethylamine and 200 mL of dehydrated pyridine were added and dissolved by stirring. After continuing to flow nitrogen for 1 hour, 0.3 g (0.000427 mol) of dichlorobis (triphenylphosphine) palladium was quickly added and heated to reflux for 1 hour in an oil bath. Thereafter, triethylamine and pyridine were distilled off under reduced pressure to obtain a viscous brown solution. This was poured into 500 mL of water, and the precipitated solid was collected by filtration, and further washed twice with 500 mL of water, 500 mL of 5 mol / L hydrochloric acid, and 500 mL of water. The solid was dried under reduced pressure at 50 ° C. to obtain 121.5 g of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne (yield 86%).

(3) [Synthesis of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt from 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne]
In a 5 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, 3 L of n-butanol and 226 g (2.72 mol) of potassium hydroxide (85%) were charged and dissolved by heating under reflux. To this was added 120 g (0.341 mol) of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne obtained above, and the mixture was heated to reflux for 30 minutes. This was cooled in an ice bath, and the precipitated crystals were collected by filtration. The crystals were washed twice with 1 L of ethanol and dried under reduced pressure at 60 ° C. to obtain 132.49 g of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt (97%).
(4) [Synthesis of 5- (2- (1-adamantyl) ethynyl) isophthalic acid from 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt]
7.6 g (0.019 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt obtained above was dissolved in 20 mL of ion-exchanged water and filtered through 5C filter paper to remove insoluble matter. Removed. To this filtrate, 5 mol / L hydrochloric acid was added with stirring until the pH reached 1. The precipitated solid was collected by filtration, and further washed with ion-exchanged water and filtered twice. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 6.1 g of 5- (2- (1-adamantyl) ethynyl) isophthalic acid (yield 99.5%).
Appearance: White powder IR: 1710-1680 cm ⁻¹ (carboxylic acid), 2260-2190 cm ⁻¹ (ethynyl group)
Elemental analysis: Theoretical value C: 74.06% H: 6.21% O: 19.73%, measured value C: 74.12% H: 6.14% O: 19.74%

(5) [Synthesis of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dichloride from 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt]
To a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 96.1 g (0.24 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt obtained above and 1 , 2-dichloroethane 400 mL was charged and cooled to 0 ° C. To this, 391 g (4.5 mol) of thionyl chloride was added dropwise at 5 ° C. or less over 1 hour. Thereafter, 4 mL of dimethylformamide and 4 g of hydroquinone were added, and the mixture was stirred at 45 to 50 ° C. for 3 hours. After cooling, the crystals formed during cooling were removed by filtration, and the crystals were washed with 150 mL of chloroform. The filtrate and the washing solution were combined and concentrated under reduced pressure at 40 ° C. or lower, and the resulting residue was extracted and filtered twice with 200 mL of diethyl ether. Diethyl ether was distilled off from the extract under reduced pressure to obtain a semisolid crude product. This was washed with dry n-hexane and then recrystallized with diethyl ether to obtain 16.5 g of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dichloride (yield) 19%).
Appearance: White powder IR: 1800-1770 cm ⁻¹ (carboxylic acid chloride), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 290 (M ⁺ -2Cl)
Elemental analysis: Theoretical value C: 66.49% H: 5.02% Cl: 19.63 O: 8.86%, measured value C: 66.41% H: 5.08% Cl: 19.70 O: 8.81%

(Synthesis Example 23)
[Synthesis of 4,6-di (1-adamantyl) -1,3-bis (4-amino-phenoxy) benzene]
In a 300 mL eggplant flask, 2,6- (1-adamantyl) -1,3-dihydroxybenzene 22.0 g (58.1 mmol) obtained in Synthesis Example 1 and 17.2 g (122 mmol) of 4-fluoronitrobenzene, Potassium carbonate 32.1 g (233 mmol), N, N-dimethylformamide 180 mL and a stirring bar were added, and the mixture was heated and stirred at 135 ° C. for 12 hours under a nitrogen stream. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, further stirred in 1 L of ion exchange water for 1 hour, and then dried under reduced pressure, whereby 4,6-di (1-adamantyl) -1,3-bis (4-nitro -30.8 g (49.6 mmol; yield 85.4%) of benzene were obtained.

Next, 29.1 g (46.8 mmol) of 4,6-di (1-adamantyl) -1,3-bis (4-nitro-phenoxy) benzene obtained above was placed in a 300 mL eggplant flask. 1.49 g (1.40 mmol) of activated carbon, 273 mL of N, N-dimethylformamide and a stirrer were added, and the mixture was stirred at 25 ° C. for 24 hours in a hydrogen atmosphere. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, further stirred in 1 L of ion exchange water for 1 hour, and then dried under reduced pressure, whereby 4,6-di (1-adamantyl) -1,3-bis (4-amino- 22.3 g (39.7 mmol; yield 84.9%) of phenoxy) benzene was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 561 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 81.39; H, 7.91; N, 5.00; O, 5.71, measured value (/%): C, 81.35; H, 7 .88; N, 5.03; O, 5.74

(Synthesis Example 24)
[Synthesis of 2,7-di (1-adamantyl) -fluorene-9,9-bis (4-aniline)]
In a 500 mL four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, 44.9 g (100 mmol) of 2,7-diadamantylfluorenone obtained in Synthesis Example 5 and 27.9 g (300 mmol) of aniline were obtained. The sample was weighed, 203 mL of Eaton's reagent (7.7 wt% diphosphorus pentoxide in methanesulfonic acid) was added, and the mixture was heated at 150 ° C. for 12 hours in a nitrogen atmosphere. After the reaction solution returned to room temperature, 100 mL of ion exchange water was slowly added. Thereafter, the reaction solution was transferred to a separatory funnel, adjusted to pH 7 with sodium hydroxide, extracted with 100 mL of ethyl acetate three times, dried over magnesium sulfate, and then ethyl acetate was distilled off with an evaporator. The obtained crude product was purified by column chromatography (hexane / ethyl acetate = 4/1) to give 2,7-di (1-adamantyl) fluorene-9,9-bis (4-aniline) 51. 0.2 g was obtained (83 mmol, yield 83%).
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 617 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 87.62; H, 7.84; N, 4.54, Actual value (/%): C, 87.64; H, 7.87; N, 4 .49;

(Synthesis Example 25)
[9,9-bis (3,4-dicarboxyphenyl) -2,7-diadamantyl-fluorene-dianhydride]
In a 500 mL four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 66.4 g (0.148 mol) of 2,7-diadamantylfluorenone obtained in Synthesis Example 5 and 47.1 g of o-xylene (0 .444 mol (3-fold mol)) was weighed out, 203 mL of Eaton's reagent (7.7 wt% diphosphorus pentoxide in methanesulfonic acid) was added, and the mixture was heated at 150 ° C. for 12 hours in a nitrogen atmosphere. After the reaction solution returned to room temperature, 30 mL of ion exchange water was slowly added. Thereafter, the reaction solution was transferred to a separatory funnel, extracted three times with 20 mL of ethyl acetate, dried over magnesium sulfate, and then ethyl acetate was distilled off with an evaporator. The obtained crude product was purified by column chromatography (hexane / ethyl acetate = 4/1) to give 9,9-bis (3,4-dimethyl-phenyl) -2,7-diadamantyl-fluorene. 77.2 g was obtained (0.12 mol, yield 80.9%).

Next, the 9,9-bis (3,4-dimethyl-phenyl) -2,7-diadamantyl-fluorene 77 obtained above was added to a 3 L 4-neck Separa flask equipped with a thermometer, a stirrer and a reflux tube. .2 g (0.12 mol), potassium permanganate 89.0 g (0.563 mol), 1 L of pyridine and 100 mL of water were charged and heated to reflux at 100 ° C.
Refluxing was started and 38.7 g (0.245 mol) of potassium permanganate and 160 mL of water were added every 30 minutes. This was repeated a total of 4 times. Five hours after the start of reflux, 160 mL of water was added. Thereafter, the mixture was further heated to reflux for 6 hours. The precipitate was filtered hot, 400 mL of 6 mol / l hydrochloric acid was added to the concentrated filtrate, and the resulting precipitate was collected by filtration and dried to give 9,9-bis (3,4). -Dicarboxy-phenyl) -2,7-diadamantyl-fluorene 36.6 g was obtained (0.048 mol, 40% yield).
Next, the 9,9-bis (3,4-dicarboxy-phenyl) -2,7-diadamantyl-fluorene obtained above was added to a 500 mL four-necked Separa flask equipped with a thermometer, a stirrer and a reflux tube. 35.1 g (0.046 mol) and acetic anhydride 34.5 g (0.276 mol) are charged, and 9,9-bis (3,4-dicarboxy-phenyl) -2,7-diadamantyl-fluorene is completely dissolved. Gently refluxed until Thereafter, the mixture is further heated for about 10 minutes, and the reaction mixture is poured onto a porcelain iron and allowed to cool. When solidified, it was crushed and filtered. The resulting crystal mass was crushed in 75 mL of ether without alcohol and filtered again. After drying in air for a short time, drying to a constant weight at 105 ° C., 99.7 g of 9,9-bis (3,4-dicarboxy-phenyl) -2,7-diadamantyl-fluorene dianhydride (0.0409 mol, yield 89.0%) was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Light yellow solid MS (FD) (m / z): 727 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 80.97; H, 5.82, O, 13.21, Measured value (/%): C, 80.95; H, 5.88; O, 13 .17;

(Synthesis Example 26)
[1,3-bis (3,4-dicarboxyphenoxy) -4,6-bis [(3- (1-adamantyl)-(1-adamantyl))-benzene-dianhydride]
4,6-di [3- (1-adamantyl)-(1-adamantyl)]-obtained in Synthesis Example 15 was added to a 500 mL four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer. First, 35.9 g (55.5 mmol) of 1,3-dihydroxybenzene, 19.0 g (114.5 mmol) of dimethyl 4-fluorophthalate, and 150 mL of N, N-dimethylformamide were added, and further 19.1 g (138.138) of potassium carbonate. 1 mmol) was added. After stirring at 135 ° C. for 12 hours, the reaction solution was filtered. The filtrate was added dropwise to 1000 mL of ion exchange water. The precipitated solid was washed twice with 1000 mL of methanol and dried under reduced pressure at 50 ° C. for 2 days, whereby 1,3-bis (3,4-dicarboxydimethyl-phenoxy) -4,6-bis [(3- 51.8 g (50.2 mmol, yield 90.5%) of (1-adamantyl)-(1-adamantyl)]-benzene was obtained.

  In a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, 500 mL of n-butanol and 33.0 g (0.5 mol) of potassium hydroxide (85%) were charged and dissolved by heating under reflux. To this, 1,3-bis (3,4-dicarboxydimethyl-phenoxy) -4,6-bis [(3- (1-adamantyl)-(1-adamantyl))-obtained by repeating the above operation 51.6 g (50 mmol) of benzene was added and heated to reflux for 30 minutes. This was cooled in an ice bath, and the precipitated crystals were collected by filtration. The crystals were dissolved in 100 mL of ion exchange water, and 5 mol / L hydrochloric acid was added with stirring until the pH reached 1. The precipitated solid was collected by filtration, washed with ion exchange water, and filtration was repeated twice. Further, washing with ethanol was repeated twice. The obtained solid was dried at 50 ° C. under reduced pressure to give 1,3-bis (3,4-dicarboxy-phenoxy) -4,6-bis [(3- (1-adamantyl)-(1-adamantyl). )]-Benzene (45.5 g, 46.7 mmol, yield 93.3%) was obtained.

Next, to a 500 mL four-necked Separa flask equipped with a thermometer, a stirrer, and a reflux tube, 1,3-bis (3,4-dicarboxy-phenoxy) -4,6-bis [(3 -(1-adamantyl)-(1-adamantyl))-benzene 44.9 g (0.046 mol) and acetic anhydride 34.5 g (0.276 mol) were charged, and 1,3-bis (3,4-dicarboxy- The mixture was gently refluxed until the phenoxy) -4,6-bis [(3- (1-adamantyl)-(1-adamantyl))-benzene was completely dissolved. Thereafter, the mixture is further heated for about 10 minutes, and the reaction mixture is poured onto a porcelain iron and allowed to cool. When solidified, it was crushed and filtered. The resulting crystal mass was crushed in 75 mL of ether without alcohol and filtered again. After drying in air for a short time, it is dried at 105 ° C. to a constant weight, and 1,3-bis (3,4-dicarboxy-phenoxy) -4,6-bis [(3- (1-adamantyl) There was obtained 37.8 g (0.0409 mol, yield 87.4%) of-(1-adamantyl))-benzene dianhydride.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Light yellow solid MS (FD) (m / z): 938 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 79.29; H, 7.08, O, 13.63, Actual value (/%): C, 79.32; H, 7.05; O, 13 .63;

[Production of benzoxazole resin precursor]
In a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 4,6-di (1-adamantyl) -1,3-bis (4- Amino-3-hydroxyphenoxy) benzene (56.3 g, 0.095 mol) was dissolved in dried N-methyl-2-pyrrolidone (800 g), and pyridine (17.4 g, 0.22 mol) was added. After cooling, 65.6 g (0.10 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dichloride obtained in Synthesis Example 13 was added little by little. . After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, returned to room temperature, and stirred at room temperature for 5 hours. Thereafter, the reaction solution was dropped into 4 L of distilled water with small droplets, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 21,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required by polystyrene conversion using Tosoh Corporation GPC.

[Manufacture of resin film]
The benzoxazole resin precursor was dissolved in N-methyl-2-pyrrolidone and filtered through a Teflon (registered trademark) filter to obtain a varnish for coating. This varnish was applied onto a silicon wafer using a spin coater. Then, it heated at 90 degreeC / 1 minute and 400 degreeC / 1 hour in oven of nitrogen atmosphere, and obtained the resin film.

In the production of the benzoxazole resin precursor of Example 1, instead of 56.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene In addition, 81.8 g (0.095 mol) of 4,6-di (3- (1-adamantyl) -1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene obtained in Synthesis Example 3 was obtained. ), And instead of 65.6 g (0.10 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dichloride, it was obtained in Synthesis Example 15. 92.4 g (0.10 mol) of 4,6-di [(3- (1-adamantyl)-(1-adamantyl)]-1,3-bis (4-carboxy-phenoxy) benzene dichloride was used. Outside, the reaction was carried out in the same manner as in Example 1 to obtain the benzoxazole resin precursor.
It was 25,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In the production of the benzoxazole resin precursor of Example 1, instead of 56.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene In addition, 61.6 g (0.095 mol) of 9,9-bis (3-amino-4-hydroxy-phenyl) -2,7-di (1-adamantyl) -fluorene obtained in Synthesis Example 5 was used. 2,7-diadamantylfluorene obtained in Synthesis Example 17 in place of 65.6 g (0.10 mol) of 1,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dichloride A reaction was carried out in the same manner as in Example 1 except that 71.2 g (0.10 mol) of -9,9-bisbenzoic acid dichloride was used to obtain a benzoxazole resin precursor.
It was 22,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In the production of the benzoxazole resin precursor of Example 1, instead of 56.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene In addition, 66.8 g (0.095 mol) of 9,9-bis (3-amino-4-hydroxy-phenyl) -2,7-di (3,5-dimethyl-1-adamantyl) -fluorene obtained in Synthesis Example 6 was obtained. 2), which was obtained in Synthesis Example 18 instead of 65.6 g (0.10 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dichloride. , 7-di (3,5-dimethyl-1-adamantyl) fluorene-9,9-bisbenzoic acid dichloride was used in the same manner as in Example 1 except that 76.7 g (0.10 mol) was used. Ben Oxazol resin precursor.
It was 24,500 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In the production of the benzoxazole resin precursor of Example 1, instead of 56.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene In addition, 79.1 g (0.095 mol) of 9,9-bis [4- (3-hydroxy-4-amino-phenoxy) -phenyl] -2,7-di (1-adamantyl) -fluorene obtained in Synthesis Example 7 was obtained. 9) obtained in Synthesis Example 19 instead of 65.6 g (0.10 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dichloride. , 9-bis [4- (4-carboxy-phenoxy) -phenyl] -2,7-di (1-adamantyl) -fluorene dichloride, except that 89.6 g (0.10 mol) was used. The reaction was conducted in the same manner as to give the benzoxazole resin precursor.
It was 27,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In the production of the benzoxazole resin precursor of Example 1, instead of 56.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene 51.3 g (0.095 mol) of 2,2′-dihydroxy-3,3′-diamino-5,5′-bis (3,5-dimethyl-1-adamantyl) -biphenyl obtained in Synthesis Example 9 was added. And 9,9 obtained in Synthesis Example 20 instead of 65.6 g (0.10 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dichloride. Except for using 95.2 g (0.10 mol) of bis [4- (4-carboxy-phenoxy) -phenyl] -2,7-di (3,5-dimethyl-1-adamantyl) -fluorene dichloride , The reaction was conducted in the same manner as in Example 1 to give the benzoxazole resin precursor.
It was 24,500 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In the production of the benzoxazole resin precursor of Example 1, instead of 56.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene In addition, 46.0 g of 2,2′-dihydroxy-3,3′-diamino-5,5′-bis [(3- (1-adamantyl)-(1-adamantyl))-biphenyl obtained in Synthesis Example 8 ( 0.095 mol), and instead of 65.6 g (0.10 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dichloride in Synthesis Example 21 100.0 g of 2,2′-bis [(4-carboxy-phenoxy) -phenyl] -5,5′-bis [3- (1-adamantyl)-(1-adamantyl)]-biphenyl dichloride obtained ( 0.1 The reaction was carried out in the same manner as in Example 1 except that 0 mol) was used to obtain a benzoxazole resin precursor.
It was 26,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In the production of the benzoxazole resin precursor of Example 1, instead of 56.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene 2,2′-bis [4- (3-hydroxy-4-amino-phenoxy)]-5,5′-bis [3- (1-adamantyl)-(1-adamantyl) obtained in Synthesis Example 11 The reaction was carried out in the same manner as in Example 1 except that 89.0 g (0.095 mol) of biphenyl was used to obtain a benzoxazole resin precursor.
It was 24,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In the production of the benzoxazole resin precursor of Example 1, instead of 56.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene In addition, 64 g (0.095 mol) of 4,6-di (3,5-dimethyl-1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene obtained in Synthesis Example 2 was used. Furthermore, instead of 65.6 g (0.10 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dichloride, 4,6-di-dioxide obtained in Synthesis Example 14 was used. The reaction was carried out in the same manner as in Example 1 except that 71 g (0.10 mol) of (3,5-dimethyl-1-adamantyl) -1,3-bis (4-carboxy-phenoxy) benzene dichloride was used. To give the benzoxazole resin precursor.
It was 20,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In the production of the benzoxazole resin precursor of Example 2, instead of 56.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene 4,6-di (3- (3,5-dimethyl-1-adamantyl)-(3,5-dimethyl-1-adamantyl))-1,3-bis (4-amino) obtained in Synthesis Example 4 3-hydroxyphenoxy) benzene (92 g, 0.095 mol) was used, and 4,6-di [(3- (1-adamantyl)-(1-adamantyl))-1,3-bis (4-carboxy-phenoxy) was further used. ) 4,6-di [3- (5,7-dimethyl-1-adamantyl)-(3,5-dimethyl-1-adamantyl)]-1, obtained in Synthesis Example 16 instead of benzene dichloride 3-bis (4- Rubokishi - phenoxy) except for using benzene dichloride 103 g (0.10 mol) performs the same reaction as Example 1 to give the benzoxazole resin precursor.
It was 16,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

  In the preparation of the benzoxazole resin precursor of Example 8, 2,2′-bis [4- (3-hydroxy-4-amino) phenoxy-phenyl] -5,5′-bis [(3- (1-adamantyl) )-(1-adamantyl)) biphenyl instead of 89.0 g (0.095 mol), 2,2′-dihydroxy-3,3′-diamino-5,5′-bis (3- Benzoxazole resin was reacted in the same manner as in Example 1 except that 82 g (0.095 mol) of (5,7-dimethyl-1-adamantyl)-(3,5-dimethyl-1-adamantyl)) biphenyl was used. A precursor was obtained. It was 26,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

  In the preparation of the benzoxazole resin precursor of Example 8, 2,2′-bis [4- (3-hydroxy-4-amino) phenoxy-phenyl] -5,5′-bis (3- (1-adamantyl) Instead of 89.0 g (0.095 mol) of-(1-adamantyl) -biphenyl, 2,2′-bis [4- (3-hydroxy-4-amino) phenoxy] -5,5 obtained in Synthesis Example 12 A reaction was carried out in the same manner as in Example 1 except that 68 g (0.095 mol) of '-bis (3- (3,5-dimethyl-1-adamantyl) biphenyl was used to obtain a benzoxazole resin precursor. It was 15,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 4,6-di (3,5-dimethyl-1-adamantyl) -1, obtained in Synthesis Example 2 under a nitrogen stream, 64.8 g (0.10 mol) of 3-bis (4-amino-3-hydroxyphenoxy) benzene was dissolved in 800 g of dried N-methyl-2-pyrrolidone, and 17.4 g (0.22 mol) of pyridine was added. Thereafter, the mixture was heated to 60 ° C., and 42.8 g (0.095 mol) of 5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane-3,3′-dicarboxylic acid chloride was added little by little. did. After completion of the addition, the mixture was stirred at 60 ° C. for 3 hours. Then, 2.10 g (0.015 mol) of benzoic acid chloride was added while keeping the internal temperature at 5 ° C. or lower by using an ice bath. The reaction solution was dropped into 4 L of distilled water in small droplets, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 15,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 4,6-di (3,5-dimethyl-1-adamantyl) -1, obtained in Synthesis Example 2 under a nitrogen stream, 64.8 g (0.10 mol) of 3-bis (4-amino-3-hydroxyphenoxy) benzene was dissolved in 800 g of dried N-methyl-2-pyrrolidone, and 17.4 g (0.22 mol) of pyridine was added. Thereafter, the mixture was heated to 60 ° C., and 31.6 g (0.070 mol) of 5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane-3,3′-dicarboxylic acid chloride was added little by little. did. After completion of the addition, the mixture was stirred at 60 ° C. for 3 hours. Thereafter, 7.57 g (0.025 mol) of 5-phenylethynyl-isophthalic acid chloride was added little by little while keeping the internal temperature at 5 ° C. or lower in an ice bath. After the addition was completed, 2.10 g (0.015 mol) of benzoic acid chloride was added while keeping the internal temperature at 5 ° C. or lower. The reaction solution was dropped into 4 L of distilled water in small droplets, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 16,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In a separable flask equipped with a stirrer, a nitrogen inlet tube, and a raw material inlet, 4,3.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-phenoxy) benzene Was dissolved in 800 g of dried N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP). The solution was cooled to 10 ° C. under dry nitrogen and charged with 72.7 g (0.1 mol) of 9,9-bis (3,4-dicarboxyphenyl) -2,7-diadamantyl-fluorene-dianhydride. . Five hours after the addition, the temperature was returned to room temperature, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was dropped into 4 L of distilled water as small droplets, and the precipitate was collected and dried to obtain a polyimide resin precursor.
It was 24,000 when the number average molecular weight (Mn) of the obtained polyimide resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

In a separable flask equipped with a stirrer, a nitrogen inlet tube, and a raw material charging port, 58.6 g (0.095 mol) of 2,7-di (1-adamantane) -fluorene-9,9-bis (4-aniline) was added. Dissolve in 1 L of dried N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP). The solution was cooled to 10 ° C. under dry nitrogen and 1,3-bis (3,4-dicarboxyphenoxy) -4,6-bis [(3- (1-adamantyl)-(1-adamantyl))-benzene -93.9 g (0.1 mol) of dianhydride was added. Five hours after the addition, the temperature was returned to room temperature, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was dropped into 4 L of distilled water as small droplets, and the precipitate was collected and dried to obtain a polyimide resin precursor.
It was 24,000 when the number average molecular weight (Mn) of the obtained polyimide resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

(Comparative Example 1)
In the production of the benzoxazole resin precursor of Example 1, instead of 56.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene In addition, 20.6 g (0.095 mol) of 3,3′-dihydroxy-4,4′-diamino-biphenyl was used, and 4,6-di (1-adamantyl) -1,3-bis (4-carboxy-) was used. The reaction was conducted in the same manner as in Example 1 except that 20.3 g of isophthalic acid dichloride (manufactured by Tokyo Chemical Industry) was used instead of 65.6 g (0.10 mol) of phenoxy) benzene dichloride, and the benzoxazole resin precursor Got the body.
It was 19,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

(Comparative Example 2)
In the production of the benzoxazole resin precursor of Example 1, instead of 56.3 g (0.095 mol) of 4,6-di (1-adamantyl) -1,3-bis (4-amino-3-hydroxyphenoxy) benzene 9,6-bis (3-amino-4-hydroxy-phenyl) -fluorene (36.1 g, 0.095 mol) and 4,6-di (1-adamantyl) -1,3-bis (4 -Carboxy-phenoxy) Examples except that 38.7 g (0.1 mol) of 1,3-bis (4-carboxy-phenoxy) -benzene were used instead of 65.6 g (0.10 mol) of benzene dichloride. Reaction was performed in the same manner as in 1 to obtain a benzoxazole resin precursor.
It was 20,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.

(Comparative Example 3)
In a separable flask equipped with a stirrer, a nitrogen inlet tube, and a raw material inlet, 10.3 g (0.095 mol) of m-phenylenediamine was dissolved in 300 g of dried N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP). . Under a nitrogen stream, the solution was cooled to 10 ° C., and 29.4 g (0.1 mol) of biphenyltetracarboxylic dianhydride was added. Five hours after the addition, the temperature was returned to room temperature, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was dropped into 4 L of distilled water as small droplets, and the precipitate was collected and dried to obtain a polyimide resin precursor.
It was 20,000 when the number average molecular weight (Mn) of the obtained polyimide resin precursor was calculated | required by polystyrene conversion using Tosoh Corporation GPC.

(Comparative Example 4)
N-methyl-2-pyrrolidone obtained by drying 33.1 g (0.095 mol) of fluorene-9,9-bis (4-aniline) in a separable flask equipped with a stirrer, a nitrogen inlet tube and a raw material inlet Dissolve in 300 g (abbreviated as NMP). The solution was cooled to 10 ° C. under dry nitrogen and charged with 40.2 g (0.1 mol) of 2,4-bis [(3,4-dicarboxy) -phenoxy] -benzene dianhydride. Five hours after the addition, the temperature was returned to room temperature, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was dropped into 4 L of distilled water as small droplets, and the precipitate was collected and dried to obtain a polyimide resin precursor.
It was 23,000 when the number average molecular weight (Mn) of the obtained polyimide resin precursor was calculated | required by polystyrene conversion using Tosoh Corporation GPC.

The following evaluation was performed about the resin film obtained in Examples 1-16 and Comparative Examples 1-4. The evaluation items are shown together with the method. The obtained results are shown in Table 1.
1. Solubility 1 g of polybenzoxazole resin precursor or polyimide resin precursor and 3 g of N-methyl-2-pyrrolidone are precisely weighed in a glass sample container with a lid, and the presence or absence of insoluble matter after stirring for 1 hour with a stir bar Judged by.

2. Heat resistance Heat resistance was evaluated by glass transition temperature and thermal decomposition temperature. The glass transition temperature was measured with a dynamic viscoelasticity measuring device (DMS6100 manufactured by Seiko Instruments Inc.) under a nitrogen stream of 300 mL / min under conditions of a temperature rising rate of 3 ° C./min and a frequency of 1 Hz. The peak top temperature of tan δ was defined as the glass transition temperature.
The thermal decomposition temperature was determined by using a TG / DTA measuring device (TG / DTA220 manufactured by Seiko Instruments Inc.) under a nitrogen stream of 200 mL / min and a temperature increase rate of 10 ° C./min. The temperature at which the weight loss reached 5% was defined as the thermal decomposition temperature.

3. Relative permittivity Based on JIS-K6911, the capacity of the adhesive film for a semiconductor was measured using a HP-4284A Precision LCR meter manufactured by Hewlett-Packard Co. at a frequency of 100 kHz, and the relative permittivity was calculated by the following formula.
Relative permittivity = (capacitance measurement value × film thickness) / (vacuum permittivity × measurement area)

As apparent from Table 1, Examples 1 to 16 had high glass transition temperature and thermal decomposition temperature, and were excellent in heat resistance.
In addition, Examples 1 to 16 were soluble in a solvent, had a low dielectric constant, and were excellent in workability and dielectric properties.
Further, Comparative Example 1 was poor in solubility and could not produce a resin film, and the glass transition temperature, thermal decomposition temperature, and dielectric constant could not be measured.
In Comparative Examples 2 to 4, the thermal decomposition temperature was excellent, but the glass transition temperature was low and the dielectric constant was high.

  Next, the interlayer insulating film and the semiconductor device will be described.

[Manufacture of coating varnish and semiconductor devices]
The benzoxazole resin precursor obtained in Example 2 was dissolved in N-methyl-2-pyrrolidone and filtered through a Teflon (registered trademark) filter to obtain a coating varnish.
A silicon nitride layer is formed on a semiconductor substrate by a known method, and the coating varnish obtained as above is applied onto the silicon nitride layer by a spin coater, and 90 ° C./1 minute in an oven in a nitrogen atmosphere. Then, heat treatment was performed at 400 ° C./1 hour to form an interlayer insulating film having a thickness of 0.3 μm.
Next, a metal wiring was formed so as to form a predetermined pattern on the interlayer insulating film, thereby obtaining a semiconductor device.

[Manufacture of coating varnish and semiconductor devices]
The benzoxazole resin precursor obtained in Example 3 was dissolved in N-methyl-2-pyrrolidone and filtered through a Teflon (registered trademark) filter to obtain a coating varnish.
A silicon nitride layer is formed on a semiconductor substrate by a known method, and the coating varnish obtained as above is applied onto the silicon nitride layer by a spin coater, and 90 ° C./1 minute in an oven in a nitrogen atmosphere. Then, heat treatment was performed at 400 ° C./1 hour to form an interlayer insulating film having a thickness of 0.3 μm.
Next, a metal wiring was formed so as to form a predetermined pattern on the interlayer insulating film, thereby obtaining a semiconductor device.

[Manufacture of coating varnish and semiconductor devices]
The polyimide resin precursor obtained in Example 13 was dissolved in N-methyl-2-pyrrolidone and filtered through a Teflon (registered trademark) filter to obtain a coating varnish.
A silicon nitride layer is formed on a semiconductor substrate by a known method, and the coating varnish obtained as above is applied onto the silicon nitride layer by a spin coater, and is 90 ° C./1 minute in an oven in a nitrogen atmosphere. Then, heat treatment was performed at 350 ° C./1 hour to form an interlayer insulating film having a thickness of 0.3 μm.
Next, a metal wiring was formed so as to form a predetermined pattern on the interlayer insulating film, thereby obtaining a semiconductor device.

The wiring delay rate was evaluated for the obtained semiconductor device.
The degree of wiring delay between a semiconductor device obtained using the interlayer insulating films of Examples 17, 18 and 19 and a semiconductor device having a SiO ₂ insulating film with the same configuration as this semiconductor device were compared. As the evaluation standard, the signal delay time obtained by conversion from the transmission frequency of the ring oscillator was adopted. As a result of comparing both, the semiconductor device obtained by the present invention has less wiring delay, the speed of Example 20 is improved by about 20%, the speed of Example 18 is improved by about 15%, and Example 19 was confirmed to have a speed increase of about 10%.

  The resin composition, polyimide resin composition, polybenzoxazole resin composition, varnish, resin film, and semiconductor device using these of the present invention constitute a low dielectric constant interlayer insulating film excellent in heat resistance and electrical characteristics. It can be used as an organic material (particularly a resin precursor) or as a semiconductor device provided with a low dielectric constant interlayer insulating film having excellent heat resistance and electrical characteristics.

FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Silicon nitride film 3 Interlayer insulation film 4 Copper wiring layer 5 Modification process layer 6 Barrier layer 7 Hard mask layer 100 Semiconductor device

Claims (10)

The resin composition containing the compound which has a structure represented by General formula (1).

[In the formula (1), Ar represents an aromatic group, and a represents 1 . R ₁₁ represents hydrogen or an organic group having 1 or more carbon atoms, and when q is an integer of 2 or more, R ₁₁ may be the same as or different from each other. R ₁ to R ₅ and R ₆ to R ₁₀ each have at least one binding site to Ar in each benzene ring, and other than that, hydrogen, a group having an alicyclic structure, and the alicyclic structure It represents any one of an organic group having 1 to 10 carbon atoms other than the group, a hydroxyl group and a carboxyl group , and R ₂ or R ₃ , and R ₇ or R ₈ represents a carboxyl group . R ₁₁ , R ₁ to R ₅ and R ₆ to R ₁₀ each represent a group having an alicyclic structure. q is an integer of 1 or more. X is, - NHCO - show the. ] The compound having a structure represented by the general formula (1) has an organic group having 1 or more carbon atoms as R ₁₁ , and at least one of the organic groups is a group having an alicyclic structure. 2. The resin composition according to 1 . Compounds having the structure represented by the general formula (1) is claimed in claim 1 or 2 are those having a group selected from the structures represented by the general formula (2) as Ar in the general formula (1) Resin composition.

[Wherein Y represents any of —O—, —S—, —OCO— and —COO—. ] It said group having an alicyclic structure, the resin composition according to any one of claims 1 to 3 is a group having an adamantane structure. The resin composition according to claim 4 , wherein the group having an adamantane structure has an alkyl group having 1 to 20 carbon atoms. The resin composition according to any one of claims 1 to 5 , wherein the resin composition is obtained by dehydrating and ring-closing a compound having a structure represented by the general formula (1) in the resin composition. The polyimide resin composition obtained by dehydrating and ring-closing the compound which has a structure represented by the said General formula (1) in the resin composition in any one of Claims 1 thru | or 5 . The resin composition according to any one of claims 1 to 6, varnish obtained Ri by polyimide resin composition according to claim 7. The resin composition according to any one of claims 1 to 6, the polyimide resin composition monomers other claim 7 varnish according to claim 8, the resin film obtained by heat treatment. A semiconductor device comprising the resin film according to claim 9 .

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